Metal-ligand complex catalyzed processes

ABSTRACT

This invention relates to a process for separating one or more organophosphorus ligand degradation products, one or more reaction byproducts and one or more formylester products from a reaction product fluid comprising one or more unreacted unsaturated ester reactants, a metal-organophoshorus ligand complex catalyst, optionally free organophosphorus ligand, said one or more organophosphorus ligand degradation products, said one or more reaction byproducts, said one or more products, a nonpolar solvent and a polar solvent by phase separation wherein (i) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more products is expressed by a partition coefficient ratio Ef1 which is a value greater than about 2.5 (ii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more organophosphorus ligand degradation products is expressed by a partition coefficient ratio Ef2 which is a value greater than about 2.5, and (iii) the selectivity of the nonpolar phase for the organophosphorus ligand with respect to the one or more reaction byproducts is expressed by a partition coefficient ratio Ef3 which is a value greater than about 2.5.

RELATED APPLICATION

This application is related to copending U.S. patent application Ser.No. (D-17979), filed on an even date herewith, the disclosure of whichis incorporated herein by reference.

BRIEF DESCRIPTION OF THE INVENTION Technical Field

This invention relates to improved metal-organophosphorus ligand complexcatalyzed processes. More particularly this invention relates tometal-organophosphorus ligand complex catalyzed processes in which thedesired product, along with any organophosphorus ligand degradationproducts and reaction byproducts, can be selectively extracted andseparated from the reaction product fluid by phase separation.

BACKGROUND OF THE INVENTION

It is known in the art that various products may be produced by reactingone or more reactants in the presence of an metal-organophosphorusligand complex catalyst. However, stabilization of the catalyst andorganophosphorus ligand remains a primary concern of the art. Obviouslycatalyst stability is a key issue in the employment of any catalyst.Loss of catalyst or catalytic activity due to undesirable reactions ofthe highly expensive metal catalysts can be detrimental to theproduction of the desired product. Moreover, production costs of theproduct obviously increase when productivity of the catalyst decreases.

For instance, a cause of organophosphorus ligand degradation andcatalyst deactivation of metal-organophosphorus ligand complex catalyzedhydroformylation processes is due in part to vaporizer conditionspresent during, for example, in the vaporization employed in theseparation and recovery of the aldehyde product from the reactionproduct mixture. When using a vaporizer to facilitate separation of thealdehyde product of the process, a harsh environment of a hightemperature and a low carbon monoxide partial pressure than employedduring hydroformylation is created, and it has been found that when aorganophosphorus promoted rhodium catalyst is placed under suchvaporizer conditions, it will deactivate at an accelerated pace withtime. It is further believed that this deactivation is likely caused bythe formation of an inactive or less active rhodium species. Such isespecially evident when the carbon monoxide partial pressure is very lowor absent. It has also been observed that the rhodium becomessusceptible to precipitation under prolonged exposure to such vaporizerconditions.

For instance, it is theorized that under harsh conditions such as existin a vaporizer, the active catalyst, which under hydroformylationconditions is believed to comprise a complex of rhodium,organophosphorus ligand, carbon monoxide and hydrogen, loses at leastsome of its coordinated carbon monoxide, thereby providing a route forthe formation of such a catalytically inactive or less active rhodium.Accordingly, a successful method for preventing and/or lessening suchdegradation of the organophosphorus ligand and deactivation of thecatalyst as occur under harsh separation conditions in a vaporizer wouldbe highly desirable to the art.

Organophosphorus ligand degradation and catalyst deactivation ofmetal-organophosphorus ligand complex catalyzed hydroformylationprocesses can occur under process conditions other than vaporizerconditions. The buildup of organophosphorus ligand degradation productsas well as reaction byproducts in the reaction product fluid can have adetrimental effect on the process, e.g., decreases catalyst efficiency,raw material conversion and product selectivity. Accordingly, asuccessful method for preventing and/or lessening such buildup oforganophosphorus ligand degradation products and reaction byproducts inthe reaction product fluid would be highly desirable in the art.

DISCLOSURE OF THE INVENTION

It has now been discovered that in metal-organophosphorus ligand complexcatalyzed processes, the desired product, along with anyorganophosphorus ligand degradation products and reaction byproducts,can be selectively extracted and separated from the reaction productfluid by phase separation. By the practice of this invention, it is nowpossible to separate the desired product, along with anyorganophosphorus ligand degradation products and reaction byproducts,from the reaction product fluid without the need to use vaporizationseparation and the harsh conditions associated therewith. This inventionprovides a highly desirable separation method which prevents and/orlessens degradation of the organophosphorus ligand and deactivation ofthe catalyst as occur under harsh conditions with vaporizationseparation. This invention also provides a highly desirable separationmethod which prevents and/or lessens the buildup of organophosphorusligand degradation products and reaction byproducts in the reactionproduct fluid.

This invention relates in part to a process for separating one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof, from a reaction productfluid comprising one or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products, a nonpolar solvent and a polarsolvent, wherein said process comprises (1) mixing said reaction productfluid to obtain by phase separation a nonpolar phase comprising said oneor more unreacted unsaturated reactants, said metal-organophosphorusligand complex catalyst, said optionally free organophosphorus ligandand said nonpolar solvent and a polar phase comprising said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products and said polar solvent, and (2)recovering said polar phase from said nonpolar phase; wherein (i) theselectivity of the nonpolar phase for the organophosphorus ligand withrespect to the one or more products is expressed by the followingpartition coefficient ratio Ef1: ${Ef1} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp2}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {products}}\end{matrix}}$

in which said partition coefficient Kp1 is the ratio of theconcentration of organophosphorus ligand in the nonpolar phase afterextraction to the concentration of organophosphorus ligand in the polarphase after extraction, said partition coefficient Kp2 is the ratio ofthe concentration of products in the nonpolar phase after extraction tothe concentration of products in the polar phase after extraction, andsaid Ef1 is a value greater than about 2.5, (ii) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more organophosphorus ligand degradation products is expressed by thefollowing partition coefficient ratio Ef2: ${Ef2} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp3}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {organophosphorus}} \\{{ligand}\quad {degradation}\quad {products}}\end{matrix}}$

in which said partition coefficient Kp1 is as defined above, saidpartition coefficient Kp3 is the ratio of the concentration oforganophosphorus ligand degradation products in the nonpolar phase afterextraction to the concentration of organophosphorus ligand degradationproducts in the polar phase after extraction, and said Ef2 is a valuegreater than about 2.5, and (iii) the selectivity of the nonpolar phasefor the organophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the following partition coefficient ratioEf3: ${Ef3} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp4}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {reaction}} \\{{by}{products}}\end{matrix}}$

in which said partition coefficient Kp1 is as defined above, saidpartition coefficient Kp4 is the ratio of the concentration of reactionbyproducts in the nonpolar phase after extraction to the concentrationof reaction byproducts in the polar phase after extraction, and said Ef3is a value greater than about 2.5.

This invention also relates in part to a process for separating one ormore organophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof, from a reaction productfluid comprising one or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products and a nonpolar solvent, whereinsaid process comprises (1) mixing said reaction product fluid with apolar solvent to obtain by phase separation a nonpolar phase comprisingsaid one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand and said nonpolar solvent and a polar phasecomprising said one or more organophosphorus ligand degradationproducts, said one or more reaction byproducts, said one or moreproducts and said polar solvent, and (2) recovering said polar phasefrom said nonpolar phase; wherein (i) the selectivity of the nonpolarphase for the organophosphorus ligand with respect to the one or moreproducts is expressed by the partition coefficient ratio Ef1 definedabove which is a value greater than about 2.5, (ii) the selectivity ofthe nonpolar phase for the organophosphorus ligand with respect to theone or more organophosphorus ligand degradation products is expressed bythe partition coefficient ratio Ef2 defined above which is a valuegreater than about 2.5, and (iii) the selectivity of the nonpolar phasefor the organophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the partition coefficient ratio Ef3 definedabove which is a value greater than about 2.5.

This invention further relates in part to a process for producing one ormore products, said products comprising one or more formylesters and/orderivatives thereof, comprising: (1) reacting one or more unsaturatedreactants, said unsaturated reactants comprising one or more unsaturatedesters and/or derivatives thereof, in the presence of ametal-organophosphorus ligand complex catalyst, optionally freeorganophosphorus ligand, a nonpolar solvent and a polar solvent to forma multiphase reaction product fluid, and (2) separating said multiphasereaction product fluid to obtain at least one nonpolar phase comprisingone or more unreacted unsaturated reactants, said metal-organophosphorusligand complex catalyst, said optionally free organophosphorus ligandand said nonpolar solvent and at least one polar phase comprising one ormore organophosphorus ligand degradation products, one or more reactionbyproducts, said one or more products and said polar solvent; wherein(i) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more products isexpressed by the partition coefficient ratio Ef1 defined above which isa value greater than about 2.5, (ii) the selectivity of the at least onenonpolar phase for the organophosphorus ligand with respect to the oneor more organophosphorus ligand degradation products is expressed by thepartition coefficient ratio Ef2 defined above which is a value greaterthan about 2.5, and (iii) the selectivity of the at least one nonpolarphase for the organophosphorus ligand with respect to the one or morereaction byproducts is expressed by the partition coefficient ratio Ef3defined above which is a value greater than about 2.5.

This invention yet further relates in part to a process for producingone or more products, said products comprising one or more formylestersand/or derivatives thereof, comprising: (1) reacting one or moreunsaturated reactants, said unsaturated reactants comprising one or moreunsaturated esters and/or derivatives thereof, in the presence of ametal-organophosphorus ligand complex catalyst, optionally freeorganophosphorus ligand and a nonpolar solvent to form a reactionproduct fluid; (2) mixing said reaction product fluid with a polarsolvent to form a multiphase reaction product fluid; and (3) separatingsaid multiphase reaction product fluid to obtain at least one nonpolarphase comprising one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand and said nonpolar solvent and at least one polarphase comprising one or more organophosphorus ligand degradationproducts, one or more reaction byproducts, said one or more products andsaid polar solvent; wherein (i) the selectivity of the at least onenonpolar phase for the organophosphorus ligand with respect to the oneor more products is expressed by the partition coefficient ratio Ef1defined above which is a value greater than about 2.5, (ii) theselectivity of the at least one nonpolar phase for the organophosphorusligand with respect to the one or more organophosphorus liganddegradation products is expressed by the partition coefficient ratio Ef2defined above which is a value greater than about 2.5, and (iii) theselectivity of the at least one nonpolar phase for the organophosphorusligand with respect to the one or more reaction byproducts is expressedby the partition coefficient ratio Ef3 defined above which is a valuegreater than about 2.5.

This invention relates in part to a process for separating one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof, from a reaction productfluid comprising one or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophoshorus ligand degradation products, said one or more reactionbyproducts, said one or more products, a first nonpolar solvent and asecond nonpolar solvent, wherein said process comprises (1) mixing saidreaction product fluid to obtain by phase separation a nonpolar phasecomprising said one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand, said first nonpolar solvent and said secondnonpolar solvent and a polar phase comprising said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts and said one or more products, and (2) recovering said polarphase from said nonpolar phase; wherein (i) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more products is expressed by the partition coefficient ratio Ef1defined above which is at value greater than about 2.5, (ii) theselectivity of the nonpolar phase for the organophosphorus ligand withrespect to the one or more organophosphorus ligand degradation productsis expressed by the partition coefficient ratio Ef2 defined above whichis a value greater than about 2.5, and (iii) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more reaction byproducts is expressed by the partition coefficientratio Ef3 defined above which is a value greater than about 2.5.

This invention also relates in part to a process for separating one ormore organophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof from a reaction productfluid comprising one or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products and a first nonpolar solvent,wherein said process comprises (1) mixing said reaction product fluidwith a second nonpolar solvent to obtain by phase separation a nonpolarphase comprising said one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand, said first nonpolar solvent and said secondnonpolar solvent and a polar phase comprising said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts and said one or more products, and (2) recovering said polarphase from said nonpolar phase; wherein (i) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more products is expressed by the partition coefficient ratio Ef1defined above which is a value greater than about 2.5, (ii) theselectivity of the nonpolar phase for the organophosphorus ligand withrespect to the one or more organophosphorus ligand degradation productsis expressed by the partition coefficient ratio Ef2 defined above whichis a value greater than about 2.5, and (iii) the selectivity of thenonpolar phase for the organophoshorus ligand with respect to the one ormore reaction byproducts is expressed by the partition coefficient ratioEf3 defined above which is a value greater than about 2.5.

This invention further relates in part to a process for producing one ormore products, said products comprising one or more formylesters and/orderivatives thereof, comprising: (1) reacting one or more unsaturatedreactants, said unsaturated reactants comprising one or more unsaturatedesters and/or derivatives thereof, in the presence of ametal-organophoshorus ligand complex catalyst, optionally freeorganophosphorus ligand, a first nonpolar solvent and a second nonpolarsolvent to form a multiphase reaction product fluid; and (2) separatingsaid multiphase reaction product fluid to obtain at least one nonpolarphase comprising one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand, said first nonpolar solvent and said secondnonpolar solvent and at least one polar phase comprising one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and said one or more products; wherein (i) the selectivity ofthe at least one nonpolar phase for the organophosphorus ligand withrespect to the one or more products is expressed by the partitioncoefficient ratio Ef1 defined above which is a value greater than about2.5, (ii) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more organophosphorusligand degradation products is expressed by the partition coefficientratio Ef2 defined above which is a value greater than about 2.5, and(iii) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the partition coefficient ratio Ef3 definedabove which is a value greater than about 2.5.

This invention yet further relates in part to a process for producingone or more products, said products comprising one or more formylestersand/or derivatives thereof, comprising: (1) reacting one or moreunsaturated reactants, said unsaturated reactants comprising one or moreunsaturated esters and/or derivatives thereof, in the presence of ametal-organophosphorus ligand complex catalyst, optionally freeorganophosphorus ligand and a first nonpolar solvent to form a reactionproduct fluid; (2) mixing said reaction product fluid with a secondnonpolar solvent to form a multiphase reaction product fluid; and (3)separating said multiphase reaction product fluid to obtain at least onenonpolar phase comprising one or more unreacted unsaturated reactants,said metal-organophosphorus ligand complex catalyst, said optionallyfree organophosphorus ligand, said first nonpolar solvent and saidsecond nonpolar solvent and at least one polar phase comprising one ormore organophosphorus ligand degradation products, one or more reactionbyproducts and said one or more products; wherein (i) the selectivity ofthe at least one nonpolar phase for the organophosphorus ligand withrespect to the one or more products is expressed by the partitioncoefficient ratio Ef1 defined above which is a value greater than about2.5, (ii) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more organophosphorusligand degradation products is expressed by the partition coefficientratio Ef2 defined above which is a value greater than about 2.5, and(iii) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the partition coefficient ratio Ef3 definedabove which is a value greater than about 2.5.

This invention relates in part to a process for separating one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof, from a reaction productfluid comprising one or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products and a nonpolar solvent, whereinsaid process comprises (1) mixing said reaction product fluid to obtainby phase separation a nonpolar phase comprising said one or moreunreacted unsaturated reactants, said metal-organophosphorus ligandcomplex catalyst, said optionally free organophosphorus ligand and saidnonpolar solvent and a polar phase comprising said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts and said one or more products, and (2) recovering said polarphase from said nonpolar phase; wherein (i) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more products is expressed by the partition coefficient ratio Ef1defined above which is a value greater than about 2.5, (ii) theselectivity of the nonpolar phase for the organophosphorus ligand withrespect to the one or more organophosphorus ligand degradation productsis expressed by the partition coefficient ratio Ef2 defined above whichis a value greater than about 2.5, and (iii) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more reaction byproducts is expressed by the partition coefficientratio Ef3 defined above which is a value greater than about 2.5.

This invention also relates in part to a process for producing one ormore products, said products comprising one or more formylesters and/orderivatives thereof, comprising: (1) reacting one or more unsaturatedreactants, said unsaturated reactants comprising one or more unsaturatedesters and/or derivatives thereof, in the presence of ametal-organophosphorus ligand complex catalyst, optionally freeorganophosphorus ligand and a nonpolar solvent to form a multiphasereaction product fluid; and (2) separating said multiphase reactionproduct fluid to obtain at least one nonpolar phase comprising one ormore unreacted unsaturated reactants, said metal-organophosphorus ligandcomplex catalyst, said optionally free organophosphorus ligand and saidnonpolar solvent and at least one polar phase comprising one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and said one or more products; wherein (i) the selectivity ofthe at least one nonpolar phase for the organophosphorus ligand withrespect to the one or more products is expressed by the partitioncoefficient ratio Ef1 defined above which is a value greater than about2.5, (ii) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more organophosphorusligand degradation products is expressed by the partition coefficientratio Ef2 defined above which is a value greater than about 2.5, and(iii) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the partition coefficient ratio Ef3 definedabove which is a value greater than about 2.5.

DETAILED DESCRIPTION

The processes of this invention may be asymmetric or non-asymmetric, thepreferred processes being non-asymmetric, and may be conducted in anycontinuous or semi-continuous fashion. The extraction and separation arecritical features of this invention and may be conducted as describedherein. The processing techniques used in this invention may correspondto any of the known processing techniques heretofore employed inconventional processes. Likewise, the manner or order of addition of thereaction ingredients and catalyst are also not critical and may beaccomplished in any conventional fashion. As used herein, the term“reaction product fluid” is contemplated to include, but not limited to,a reaction mixture containing an amount of any one or more of thefollowing: (a) a metal-organophosphorus ligand complex catalyst, (b)free organophosphorus ligand, (c) product(s), organophosphorus liganddegradation product(s) and byproduct(s) formed in the reaction, (d)unreacted reactant(s), and (e) solvent(s). By the practice of thisinvention, it is now possible to extract and separate the one or moreproducts, organophosphorus ligand degradation products and reactionbyproducts from the metal-organophosphorus ligand complex catalyst andunreacted reactants without the need to use vaporization separation andthe harsh conditions associated therewith. As used herein, the term“organophosphorus ligand degradation products” is contemplated toinclude, but not limited to, any and all products resulting from thedegradation of free organophosphorus ligand and organophosphorus ligandcomplexed with metal, e.g., phosphorus-containing acids, aldehyde acids,and the like. As used herein, the term “reaction byproducts” iscontemplated to include, but not limited to, any and all byproductsresulting from the reaction of one or more reactants to give one or moreproducts, e.g., product dimers, product trimers, isomerization products,hydrogenation products, and the like.

Hyxdroformylation Step or Stage

The hydroformylation process involves converting one or more substitutedor unsubstituted unsaturated esters, e.g., esters of undecenoic acidsuch as esters of 10-undecenoic acid, to one or more substituted orunsubstituted formylesters, e.g., formylundecanoates such as11-formylundecanoates, in one or more steps or stages. As used herein,the term “hydroformylation” is contemplated to include, but is notlimited to, all permissible hydroformylation processes which involveconverting one or more substituted or unsubstituted unsaturated esters,e.g., esters of undecenoic acid, to one or more substituted orunsubstituted formylesters, e.g., formylundecanoates. In general, thehydroformylation step or stage comprises reacting one or moresubstituted or unsubstituted unsaturated esters, e.g., esters ofundecenoic acid, with carbon monoxide and hydrogen in the presence of ahydroformylation catalyst to produce one or more substituted orunsubstituted formylesters, e.g., formylundecanoates. Preferredprocesses are those involving catalyst liquid recycle hydroformylationprocesses.

In general, such catalyst liquid recycle hydroformylation processesinvolve the production of aldehydes by reacting an olefinic unsaturatedcompound with carbon monoxide and hydrogen in the presence of ametal-organophosphorus ligand complex catalyst in a liquid medium thatalso contains a solvent for the catalyst and ligand. Preferably freeorganophosphorus ligand is also present in the liquid hydroformylationreaction medium. The recycle procedure generally involves withdrawing aportion of the liquid reaction medium containing the catalyst andaldehyde product from the hydroformylation reactor (i.e., reactionzone), either continuously or intermittently, and recovering thealdehyde product therefrom in accordance with the separation techniquesof this invention.

In a preferred embodiment, the hydroformylation reaction mixturesemployable herein includes any mixture derived from any correspondinghydroformylation process that contains at least some amount of fourdifferent main ingredients or components i.e., the formylester product,a metal-organophosphorus ligand complex catalyst, free organophosphorusligand and an organic solubilizing agent, e.g., nonpolar solvent, forsaid catalyst and said free ligand, said ingredients corresponding tothose employed and/or produced by the hydroformylation process fromwhence the hydroformylation reaction mixture starting material may bederived. It is to be understood that the hydroformylation reactionmixture compositions employable herein can and normally will containminor amounts of additional ingredients such as those which have eitherbeen deliberately employed in the hydroformylation process or formed insitu during said process. Examples of such ingredients that can also bepresent include unreacted olefin starting material, carbon monoxide andhydrogen gases, and in situ formed type products, such as saturatedhydrocarbons and/or unreacted isomerized olefins corresponding to theolefin starting materials, and high boiling liquid aldehyde condensationbyproducts, as well as other inert co-solvent, e.g., polar solvent, typematerials or hydrocarbon additives, if employed.

The substituted or unsubstituted olefin reactants that may be employedin the hydroformylation processes include both optically active(prochiral and chiral) and non-optically active (achiral) esters ofundecenoic acid. Such olefinic unsaturated compounds can be terminallyor internally unsaturated and be of straight-chain, branched chain orcyclic structures, as well as olefin mixtures. Moreover, mixtures of twoor more different olefinic unsaturated compounds may be employed as thestarting material if desired. Preferably, the esters of undecenoic acidare prepared from castor oil by transesterification of the triglyceridewith an alcohol, followed by pyrolysis of the resulting ricinolic acidester to give heptanal and the desired ester of 10-undecenoic acid.Alternatively, the esters of undecenoic acid are prepared from castoroil by cracking castor oil to obtain 3 equivalents of heptanal and 1equivalent of a triglyceride with triple unsaturation which can behydroformylated to the desired ester of 10-undecenoic acid. See, forexample, Kirk-Othmer, Encyclopedia of Chemical Technology, FourthEdition, 1996, Vol. 5), pp. 302-320.

Preferred unsaturated reactants include unsaturated esters and/orderivatives thereof. As used herein, derivatives of unsaturated estersinclude, for example, unsaturated acids and salts of the unsaturatedacids. This invention is not intended to be limited in any manner by thepermissible derivatives of unsaturated esters.

Preferred unsaturated esters include esters of undecenoic acidrepresented by the formula

CH₂═CH—(CH₂)₇—CH₂—C(O)—OR

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving a carbon atom number sufficient to render said unsaturated estermiscible in a nonpolar solvent. Typically, R contains from 1 to about 6or 7 carbon atoms.

Illustrative of suitable substituted and unsubstituted olefinic startingmaterials include those permissible substituted and unsubstitutedunsaturated esters, including esters of undecenoic acid, described inBeilsteins Handbuch der Organischen Chemie, Springer Verlag KG, 4^(th)Edition, the pertinent portions of which are incorporated herein byreference.

Illustrative metal-organophosphorus ligand complex catalysts employablein the processes encompassed by this invention as well as methods fortheir preparation are well known in the art and include those disclosedin the below mentioned patents. In general such catalysts may bepreformed or formed in situ as described in such references and consistessentially of metal in complex combination with an organophosphorusligand. The active species may also contain carbon monoxide and/orhydrogen directly bonded to the metal.

The catalyst useful in the processes includes a metal-organophosphorusligand complex catalyst which can be optically active or non-opticallyactive. The permissible metals which make up the metal-organophosphorusligand complexes include Group 8, 9 and 10 metals selected from rhodium(Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni),palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, withthe preferred metals being rhodium, cobalt, iridium and ruthenium, morepreferably rhodium, cobalt and ruthenium, especially rhodium. Otherpermissible metals include Group 11 metals selected from copper (Cu),silver (Ag), gold (Au) and mixtures thereof, and also Group 6 metalsselected from chromium (Cr), molybdenum (Mo), tungsten (W) and mixturesthereof. Mixtures of metals from Groups 6, 8, 9, 10 and 11 may also beused in this invention. The permissible organophosphorus ligands whichmake up the metal-organophosphorus ligand complexes and freeorganophosphorus ligand include organophosphines, e.g., bisphosphinesand triorganophosphines, and organophosphites, e.g., mono-, di-, tri-and polyorganophosphites. Other permissible organophosphorus ligandsinclude, for example, organophosphonites, organophosphinites,organophosphorus amides and the like. Mixtures of such ligands may beemployed if desired in the metal-organophosphorus ligand complexcatalyst and/or free ligand and such mixtures may be the same ordifferent. This invention is not intended to be limited in any manner bythe permissible organophosphorus ligands or mixtures thereof. It is tobe noted that the successful practice of this invention does not dependand is not predicated on the exact structure of themetal-organophosphorus ligand complex species, which may be present intheir mononuclear, dinuclear and/or higher nuclearity forms. Indeed, theexact structure is not known. Although it is not intended herein to bebound to any theory of mechanistic discourse, it appears that thecatalytic species may in its simplest form consist essentially of themetal in complex combination with the organophosphorus ligand and carbonmonoxide and/or hydrogen when used.

The term “complex” as used herein and in the claims means a coordinationcompound formed by the union of one or more electronically richmolecules or atoms capable of independent existence with one or moreelectronically poor molecules or atoms, each of which is also capable ofindependent existence. For example, the organophosphorus ligandsemployable herein may possess one or more phosphorus donor atoms, eachhaving one available or unshared pair of electrons which are eachcapable of forming a coordinate covalent bond independently or possiblyin concert (e.g., via chelation) with the metal. Carbon monoxide (whichis also properly classified as a ligand) can also be present andcomplexed with the metal. The ultimate composition of the complexcatalyst may also contain an additional ligand, e.g., hydrogen or ananion satisfying the coordination sites or nuclear charge of the metal.Illustrative additional ligands include, for example, halogen (Cl, Br,I), alkyl, aryl, substituted aryl, acyl, CF₃, C₂F₅, CN, (R)₂PO andRP(O)(OH)O (wherein each R is the same or different and is a substitutedor unsubstituted hydrocarbon radical, e.g., the alkyl or aryl), acetate,acetylacetonate, SO₄, PF₄, PF₆, NO₂, NO₃, CH₃₀, CH₂=CHCH₂, CH₃CH=CHCH₂,C₆H₅, CN, CH₃CN, NO, NH₃, pyridine, (C₂H₅)₃N, mono-olefins, diolefinsand triolefins, tetrahydrofuran, and the like. It is of course to beunderstood that the complex species are preferably free of anyadditional organic ligand or anion that might poison the catalyst orhave an undue adverse effect on catalyst performance. It is preferred inthe metal-organophosphorus ligand complex catalyzed processes, e.g.,hydroformylation, that the active catalysts be free of halogen andsulfur directly bonded to the metal, although such may not be absolutelynecessary. Preferred metal-ligand complex catalysts includerhodium-organophosphine ligand complex catalysts andrhodium-organophosphite ligand complex catalysts.

The number of available coordination sites on such metals is well knownin the art. Thus the catalytic species may comprise a complex catalystmixture, in their monomeric, dimeric or higher nuclearity forms, whichare preferably characterized by at least one organophosphorus-containingmolecule complexed per one molecule of metal, e.g., rhodium. Forinstance, it is considered that the catalytic species of the preferredcatalyst employed in a hydroformylation reaction may be complexed withcarbon monoxide and hydrogen in addition to the organophosphorus ligandsin view of the carbon monoxide and hydrogen gas employed by thehydroformylation reaction.

The organophosphines and organophosphites that may serve as the ligandof the metal-organophosphorus ligand complex catalyst and/or free ligandof the processes of this invention may be of the achiral (opticallyinactive) or chiral (optically active) type and are well known in theart. By “free ligand” is meant ligand that is not complexed with (tiedto or bound to) the metal, e.g., metal atom, of the complex catalyst. Asnoted herein, the processes of this invention and especially thehydroformylation process may be carried out in the presence of freeorganophosphorus ligand. Achiral organophosphines and organophosphitesare preferred.

Among the organophosphines that may serve as the ligand of themetal-organophosphine complex catalyst and/or free organophosphineligand of the reaction mixture starting materials aretriorganophosphines, trialkylphosphines, alkyldiarylphosphines,dialkylarylphosphines, dicycloalkylarylphosphines,cycloalkyldiarylphosphines, trialkylphosphines, trialkarylphosphines,tricycloalkylphosphines, and triarylphosphines, alkyl and/or arylbisphosphines and bisphosphine mono oxides, and the like. Of course anyof the hydrocarbon radicals of such tertiary non-ionic organophosphinesmay he substituted if desired, with any suitable substituent that doesnot unduly adversely affect the desired result of the hydroformylationreaction. The organophosphine ligands employable in the reactions and/ormethods for their preparation are known in the art.

Illustrative triorganophosphine ligands may be represented by theformula:

wherein each R¹ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical, e.g., an alkyl or arylradical. Suitable hydrocarbon radicals may contain from 1 to 24 carbonatoms or greater. Illustrative substituent groups that may be present onthe aryl radicals include, for example, alkyl radicals, alkoxy radicals,silyl radicals such as —Si(R²)₃; amino radicals such as —N(R²)₂; acylradicals such as —C(O)R²; carboxy radicals such as —C(O)OR²; acyloxyradicals such as —C(O)R²; amido radicals such as —C(O)N(R²)₂ and—N(R²)C(O)R²; sulfonyl radicals such as —SO₂R²; ether radicals such as—OR²; sulfinyl radicals such as —SOR²; sulfenyl radicals such as —SR₂ aswell as halogen, nitro, cyano, trifluoromethyl and hydroxy radicals, andthe like, wherein each R² individually represents the same or differentsubstituted or unsubstituted monovalent hydrocarbon radical, with theproviso that in amino substituents such as —N(R²)₂, each R² takentogether can also represent a divalent bridging group that forms aheterocyclic radical with the nitrogen atom and in amido substituentssuch as C(O)N(R²)₂ and —N(R²)C(O)R² each —R² bonded to N can also behydrogen. Illustrative alkyl radicals include, for example, methyl,ethyl, propyl, butyl and the like. Illustrative aryl radicals include,for example, phenyl, naphthyl, diphenyl, fluorophenyl, difluorophenyl,benzoyloxyphenyl, carboethoxyphenyl, acetylphenyl, ethoxyphenyl,phenoxyphenyl, hydroxyphenyl; carboxyphenyl, trifluoromethylphenylmethoxyethylphenyl, acetamidophenyl, dimethylcarbamylphenyl, tolyl,xylyl, and the like.

Illustrative specific organophosphines include, for exampletriphenylphosphine, tris-p-tolyl phosphine,tris-p-methoxyphenylphosphine, tris-p-fluorophenylphosphine,tris-p)-chlorophenylphosphine, tris-dimethylaminophenylphosphine,propyldiphenylphosphine, t-butyldiphenylphosphine,butyldiphenylphosphine, n-hexyldiphenylphoshine,cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine,tricyclohexylphosphine, tribenzylphosphine as well as the alkali andalkaline earth metal salts of sulfonated triphenylphosphines, forexample, of (tri-m-sulfophenyl)phosphine and of(m-sulfophenyl)diphenyl-phosphine and the like.

More particularly, illustrative metal-organophosphine complex catalystsand illustrative free organophosphine ligands include, for example,those disclosed in U.S. Pat. Nos. 3,527,8099; 4,148,830; 4,247,486;4,283,562; 4,400,548; 4,482,749 and 4,861,918, the disclosures of whichare incorporated herein by reference.

Among the organophosphites that may serve as the ligand of themetal-organophosphite complex catalyst and/or free organophosphiteligand of the reaction mixture starting materials aremonoorganophosphites, diorganophosphites, triorganophosphites andorganopolyphosphites. The organophosphite ligands employable in thisinvention and/or methods for their preparation are known in the art.

Representative monoorganophosphites may include those having theformula:

wherein R³ represents a substituted or unsubstituted trivalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater,such as trivalent acyclic and trivalent cyclic radicals, e.g., trivalentalkylene radicals such as those derived from 1,2,2-trimethylolpropaneand the like, or trivalent cycloalkylene radicals such as those derivedfrom 1,3,5-trihydroxycyclohexane, and the like. Suchmonoorganophosphites may be found described in greater detail, forexample, in U.S. Pat. No. 4,567,306, the disclosure of which isincorporated herein by reference.

Representative diorganophosphites may include those having the formula:

wherein R⁴ represents a substituted or unsubstituted divalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater andW represents a substituted or unsubstituted monovalent hydrocarbonradical containing from 1 to 18 carbon atoms or greater.

Representative substituted and unsubstituted monovalent hydrocarbonradicals represented by W in the above formula (III) include alkyl andaryl radicals, while representative substituted and unsubstituteddivalent hydrocarbon radicals represented by R⁴ include divalent acyclicradicals and divalent aromatic radicals. Illustrative divalent acyclicradicals include, for example, alkylene, alkylene-oxy-alkylene,alkylene-NX-alkylene wherein X is hydrogen or a substituted orunsubstituted monovalent hydrocarbon radical, alkylene-S-alkylene, andcycloalkylene radicals, and the like. The more preferred divalentacyclic radicals are the divalent alkylene radicals such as disclosedmore fully, for example, in U.S. Pat. Nos. 3,415,906 and 4,567,302 andthe like, the disclosures of which are incorporated herein by reference.Illustrative divalent aromatic radicals include, for example, arylene,bisarylene, arylene-alkylene, arylene-alkylene-arylene,arylene-oxy-arylene, arylene-NX-arylene wherein X is as defined above,arylene-S-arylene, and arylene-S-alkylene, and the like. More preferablyR⁴ is a divalent aromatic radical such as disclosed more fully, forexample, in U.S. Pat. Nos. 4,599,206 and 4,717,775, and the like, thedisclosures of which ale incorporated herein by reference.

Representative of a more preferred class of diorganophosphites are thoseof the formula:

wherein W is as defined above, each Ar is the same or different andrepresents a substituted or unsubstituted aryl radical, each y is thesame or different and is a value of 0 or 1, Q represents a divalentbridging group selected from —C(R⁵)₂—, —O—, —S—, —NR⁶⁻, Si(R⁷)₂— and—CO—, wherein each R⁵ is the same or different and represents hydrogen,alkyl radicals having from 1 to 12 carbon atoms, phenyl, tolyl, andanisyl, R⁶ represents hydrogen or a methyl radical, each R⁷ is the sameor different and represents hydrogen or a methyl radical, and m is avalue of 0 or 1. Such diorganophosphites are described in greaterdetail, for example, in U.S. Pat. Nos. 4,599,206, 4,717,775 and4,835,299, the disclosures of which are incorporated herein byreference.

Representative triorganophosphites may include those having the formula:

wherein each R⁸ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical e.g., an alkyl, cycloalkyl,aryl, alkaryl and aralkyl radicals which may contain from 1 to 24 carbonatoms. Suitable hydrocarbon radicals may contain from 1 to 24 carbonatoms or greater and may include those described above for R¹ in formula(I). Illustrative triorganophosphites include, for example, trialkylphosphites, dialkylaryl phosphites, alkyldiaryl phosphites, triarylphosphites, and the like, such as, for example, trimethyl phosphite,triethyl phosphite, butyldiethyl phosphite, tri-n-propyl phosphite,tri-n-butyl phosphite, tri-2-ethylhexyl phosphite, tri-n-octylphosphite, tri-n-dodecyl phosphite, dimethylphenyl phosphite,diethylphenyl phosphite, methyldiphenyl phosphite, ethyldiphenylphosphite, triphenyl phosphite, trinaphthyl phosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)methylphosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)cyclohexylphosphite,tris(3,6-di-t-butyl-2-naphthyl)phosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)(4-biphenyl)phosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)phenylphosphite,bis(3,6,8-tri-t-butyl-2-naphthyl)(4-benzoylphenyl)phosphite,bis(3,6,8-tri-t-butyl-2-naphthyl) (4-sulfonylphenyl)phosphite, and thelike. A preferred triorganophosphite is triphenylphosphite. Suchtriorganophosphites are described in greater detail, for example, inU.S. Pat. Nos. 3,527,809 and 5,277,532, the disclosures of which areincorporated herein by reference.

Representative organopolyphosphites contain two or more tertiary(trivalent) phosphorus atoms and may include those having the formula:

wherein X¹ represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁹ is the same or different and is a divalent hydrocarbon radicalcontaining from 4 to 40 carbon atoms, each R¹⁰ is the same or differentand is a substituted or unsubstituted monovalent hydrocarbon radicalcontaining from 1 to 24 carbon atoms, a and b can be the same ordifferent and each have a value of 0 to 6, with the proviso that the sumof a+b is 2 to 6 and n equals a+b. Of course it is to be understood thatwhen a has a value of 2 or more, each R⁹ radical may be the same ordifferent, and when b has a value of 1 or more, each R¹⁰ radical mayalso be the same or different.

Representative n-valent (preferably divalent) hydrocarbon bridgingradicals represented by X¹, as well as representative divalenthydrocarbon radicals represented by R⁹ above, include both acyclicradicals and aromatic radicals, such as alkylene,alkylene-Q_(m)-alkylene, cycloalkylene, arylene, bisarylene,arylene-alkylene, and arylene-(CH₂)_(y)—Q_(m)—(CH₂)_(y)-aryleneradicals, and the like, wherein Q, m and y are as defined above forformula (V). The more preferred acyclic radicals represented by X¹ andR⁹ above are divalent alkylene radicals, while the more preferredaromatic radicals represented by X¹ and R⁹ above are divalent aryleneand bisarylene radicals, such as disclosed more fully, for example, inU.S. Pat. Nos. 4,769,498; 4,774,361: 4,885,401; 5,179,055; 5,113,022;5,202,297; 5,235,113; 5,264,616 and 5,364,950, and European PatentApplication Publication No. 662,468, and the like, the disclosures ofwhich are incorporated herein by reference. Representative monovalenthydrocarbon radicals represented by each R¹⁰ radical above include alkyland aromatic radicals.

Illustrative preferred organopolyphosphites may include bisphosphitessuch as those of formulas (VII) to (IX) below:

wherein each R⁹, R¹⁰ and X¹ of formulas (VII) to (IX) are the same asdefined above for formula (VI). Preferably, each R⁹ and X¹ represents adivalent hydrocarbon radical selected from alkylene, arylene,arylene-alkylene-arylene, and bisarylene, while each R¹⁰ represents amonovalent hydrocarbon radical selected from alkyl and aryl radicals.Organophosphite ligands of such Formulas (VI) to (IX) may be founddisclosed, for example, in U.S. Pat. Nos. 4,668,651; 4,748,261;4,769,498; 4,774,361; 4,885,401; 5,113,022; 5,179,055; 5,202,297;5,235,113; 5,254,741; 5,264,616; 5,312,996: 5,364,950; and 5,391,801;the disclosures of all of which are incorporated herein by reference.

Representative of more preferred classes of organobisphosphites arethose of the following formulas (X) to (XII):

wherein Ar, Q, R⁹, R¹⁰, X¹, m and y are as defined above. Mostpreferably X¹ represents a divalentaryl-(CH₂)_(y)—(Q)_(m)—(CH₂)_(y)-aryl radical wherein each yindividually has a value of 0 or 1; m has a value of 0 or 1 and Q is—O—, —S— or —C(R⁵)₂— wherein each R⁵ is the same or different andrepresents a hydrogen or methyl radical. More preferably each alkylradical of the above defined R¹⁰ groups may contain from 1 to 24 carbonatoms and each aryl radical of the above-defined Ar, X¹, R⁹ and R¹⁰groups of the above formulas (VI) to (XII) may contain from 6 to 18carbon atoms and said radicals may be the same or different, while thepreferred alkylene radicals of X¹ may contain from 2 to 18 carbon atomsand the preferred alkylene radicals of R⁹ may contain from 5 to 18carbon atoms. In addition, preferably the divalent Ar radicals anddivalent aryl radicals of X¹ of the above formulas are phenyleneradicals in which the bridging group represented by—(CH₂)_(y)—(Q)_(m)—(CH₂)_(y)— is bonded to said phenylene radicals inpositions that are ortho to the oxygen atoms of the formulas thatconnect the phenylene radicals to their phosphorus atom of the formulae.It is also preferred that any substituent radical when present on suchphenylene radicals be bonded in the para and/or ortho position of thephenylene radicals in relation to the oxygen atom that bonds the givensubstituted phenylene radical to its phosphorus atom.

Of course any of the R³, R⁴, R⁸, R⁹, R¹⁰, X¹, X², W, Q and Ar radicalsof such organophosphites of formulas (II) to (XII) above may besubstituted if desired, with any suitable substituent containing from 1to 30 carbon atoms that does not unduly adversely affect the desiredresult of the hydroformylation reaction. Substituents that may be onsaid radicals in addition of course to corresponding hydrocarbonradicals such as alkyl, aryl, aralkyl, alkaryl and cyclohexylsubstituents, may include for example silyl radicals such as —Si(R¹²)₃;amino radicals such as —N(R¹²)₂; phosphine radicals such as-aryl-P(R¹²)₂; acyl radicals such as —C(O)R¹²; acyloxy radicals such as—OC(O)R¹²; amido radicals such as —CON(R¹²)₂ and —N(R¹²)COR¹²; sulfonylradicals such as —SO₂R¹²; alkoxy radicals such as —OR¹²; sulfinylradicals such as —SOR¹²; sulfenyl radicals such as —SR¹²; phosphonylradicals such as —P(O)(R¹²)₂; as well as, halogen, nitro, cyano,trifluoromethyl, hydroxy radicals, and the like, wherein each R¹²radical is the same or different and represents a monovalent hydrocarbonradical having from 1 to 18 carbon atoms (e.g., alkyl, aryl, aralkyl,alkaryl and cyclohexyl radicals), with the proviso that in aminosubstituents such as —N(R¹²)₂ each R¹² taken together can also representa divalent bridging group that forms a heterocyclic radical with thenitrogen atom, and in amido substituents such as —(O)N(R¹²)₂ and—N(R¹²)COR¹² each R¹² bonded to N can also be hydrogen. Of course it isto be understood that ally of the substituted or unsubstitutedhydrocarbon radicals groups that make up a particular givenorganophosphite may be the same or different.

More specifically illustrative substituents include primary, secondaryand tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl,butyl, sec-butyl, t-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, t-amyl,iso-octyl, decyl, octadecyl, and the like; aryl radicals such as phenyl,naphthyl and the like; aralkyl radicals such as benzyl, phenylethyl,triphenylmethyl, and the like; alkaryl radicals such as tolyl, xylyl,and the like; alicyclic radicals such as cyclopentyl, cyclohexyl,1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, and the like; alkoxyradicals such as methoxy, ethoxy, propoxy, t-butoxy, —OCH₂CH₂OCH₃,—(OCH₂CH₂)₂OCH₃, —(OCH₂CH₂)₃OCH₃, and the like; aryloxy radicals such asphenoxy and the like, as well as silyl radicals such as —Si(CH₃)₃,—Si(OCH₃)₃, —Si(C₃H₇)₃, and the like; amino radicals such as —NH₂,—N(CH₃)₂, —NHCH₃, —NH(C₂H₅), and the like; arylphosphine radicals suchas —P(C₆H₅)₂, and the like; acyl radicals such as —C(O)CH₃, —C(O)C₂H₅,—C(O)C₆H₅, and the like; carbonyloxy radicals such as —C(O)OCH₃ and thelike; oxycarbonyl radicals such as —O(CO)C₆H₅, and the like; amidoradicals such as —CONH₂, —CON(CH₃)₂, —NHC(O)CH₃, and the like; sulfonylradicals such as —S(O)₂C₂H)₅ and the like; sulfinyl radicals such as—S(O)CH₃ and the like; sulfenyl radicals such as —SCH₃, SC₂H₅, —SC₆H₅,and the like; phosphonyl radicals such as —P(O)(C₆H₅)₂, —P(O)(CH₃)₂,—P(O)(C₂H₅)₂, —P(O)(C₃H₇)₂, —P(O)(C₄H₉)₂, —P(O)(C₆H₁₃)₂, —P(O)CH₃(C₆H₅),—P(O)(H)(C₆H₅), and the like.

Specific illustrative examples of organophosphorus ligands are describedin U.S. Pat. No. 5,7786,517, the disclosure of which is incorporatedherein by reference.

The metal-organophosphorus ligand complex catalysts are preferably inhomogeneous form. For instance, preformed rhodiumhydrido-carbonyl-organophosphorus ligand catalysts may be prepared andintroduced into the reaction mixture of a particular process. Morepreferably, the metal-organophosphorus ligand complex catalysts can bederived from a rhodium catalyst precursor which may be introduced intothe reaction medium for in situ formation of the active catalyst. Forexample, rhodium catalyst precursors such as rhodium dicarbonylacetylacetonate, Rh₂O₃, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Rh(NO₃)₃ and the like maybe introduced into the reaction mixture along with the organophosphorusligand for the in situ formation of the active catalyst.

As noted above, the organophosphorus ligands can be employed as both theligand of the metal-organophosphorus ligand complex catalyst, as wellas, the free organophosphorus ligand that can be present in the reactionmedium of the processes of this invention. In addition, it is to beunderstood that while the organophosphorus ligand of themetal-organophosphorus ligand complex catalyst and any excess freeorganophosphorus ligand preferably present in a given process of thisinvention are normally the same type of ligand, different types oforganophosphorus ligands, as well as, mixtures of two or more differentorganophosphorus ligands may be employed for each purpose in any givenprocess, if desired.

The amount of metal-organophosphorus ligand complex catalyst present inthe reaction medium of a given process of this invention need only bethat minimum amount necessary to provide the given metal concentrationdesired to be employed and which will furnish the basis for at leastthat catalytic amount of metal necessary to catalyze the particularprocess desired. In general, metal concentrations in the range of fromabout 1 part per million to about 10,000 parts per million, calculatedas free metal, and ligand to metal mole ratios in the catalyst solutionranging from about 1:1 or less to about 200:1 or greater, should besufficient for most processes.

As noted above, in addition to the metal-organophosphorus ligand complexcatalysts, the processes of this invention and especially thehydroformylation process can be carried out in the presence of freeorganophosphorus ligand. While the processes of this invention may becarried out in any excess amount of free organophosphorus liganddesired, the employment of free organophosphorus ligand may not beabsolutely necessary. Accordingly, in general, amounts of ligand of fromabout 1.1 or less to about 200, or higher if desired, moles per mole ofmetal (e.g., rhodium) present in the reaction medium should be suitablefor most purposes, particularly with regard to rhodium catalyzedhydroformylation; said amounts of ligand employed being the sum of boththe amount of ligand that is bound (complexed) to the metal present andthe amount of free (non-complexed) ligand present. Of course, ifdesired, make-up ligand can be supplied to the reaction medium of theprocess, at any time and in any suitable manner, to maintain apredetermined level of free ligand in the reaction medium.

The reaction conditions of the hydroformylation processes encompassed bythis invention many include any suitable type hydroformylationconditions heretofore employed for producing optically active and/ornon-optically active formylesters. For instance, the total gas pressureof hydrogen, carbon monoxide and olefin starting compound of thehydroformylation process may range from about 1 to about 10,000 psia. Ingeneral, however, it is preferred that the process be operated at atotal gas pressure of hydrogen, carbon monoxide and olefin startingcompound of less than about 2000 psia and more preferably less thanabout 1000 psia. The minimum total pressure is limited predominately bythe amount of reactants necessary to obtain a desired rate of reaction.More specifically the carbon monoxide partial pressure of thehydroformylation process of this invention is preferable from about 1 toabout 1000 psia, and more preferably from about 3 to about 800 psia,while the hydrogen partial pressure is preferably about 5 to about 500psia and more preferably from about 10 to about 300 psia. In generalH₂:CO molar ratio of gaseous hydrogen to carbon monoxide may range fromabout 1:10 to 100:1 or higher, the more preferred hydrogen to carbonmonoxide molar ratio being from about 1:10 to about 10:1. Further, thehydroformylation process may be conducted at a reaction temperature fromabout −25° C. to about 200° C. In general hydroformylation reactiontemperatures of about 50° C. to about 120° C. are preferred for alltypes of olefinic starting materials. Of course it is to be understoodthat when non-optically active formylester products are desired, achiraltype olefin starting materials and organophosphorus ligands are employedand when optically active formylester products are desired prochiral orchiral type olefin starting materials and organophosphorus ligands areemployed. Of course, it is to be also understood that thehydroformylation reaction conditions employed will be governed by thetype of formylester product desired.

The hydroformylation processes are conducted for a period of timesufficient to produce the desired formylundecanoates. The exact reactiontime employed is dependent, in part, upon factors such as temperature,pressure, nature and proportion of starting materials, and the like. Thereaction time will normally be within the range of from about one-halfto about 200 hours or more, and preferably from less than about one toabout 10 hours.

As indicated above, the processes of this invention are conducted in thepresence of a nonpolar solvent and a polar solvent, or in the presenceof a nonpolar solvent followed by mixing with a polar solvent, or in thepresence of a nonpolar solvent followed by mixing with a second nonpolarsolvent. Depending on the particular catalyst and reactants employed,suitable nonpolar solvents include, for example, alkanes, cycloalkanes,alkenes, aldehydes, ketones, ethers, esters, amines, aromatics, silanes,silicones, carbon dioxide, and the like. Examples of unsuitable nonpolarsolvents include fluorocarbons and fluorinated hydrocarbons. These areundesirable due to their high cost, risk of environmental pollution, andthe potential of forming multiphases. In an embodiment, the one or morereactants, metal-organophosphorus ligand complex catalyst, andoptionally free organophosphorus ligand exhibit sufficient solubility inthe nonpolar solvent such that phase transfer agents or surfactants arenot required.

Mixtures of one or more different nonpolar solvents may be employed ifdesired. The amount of nonpolar solvent employed is not critical to thesubject invention and need only be that amount sufficient to provide thereaction medium with the particular metal concentration desired for agiven process. In general, the amount of nonpolar solvent employed mayrange from about 5 percent by weight up to about 99 percent by weight ormore based on the total weight of the reaction mixture.

Illustrative nonpolar solvents useful in this invention include, forexample, propane, 2,2-dimethylpropane, butane, 2,2-dimethylbutane,pentane, isopropyl ether, hexane, triethylamine, heptane, octane,nonane, decane, isobutyl isobutyrate, tributylamine, undecane,2,2,4-trimethylpentyl acetate, isobutyl heptyl ketone, diisobutylketone, cyclopentane, cyclohexane, isobutylbenzene, n-nonylbenzene,n-octylbenzene, n-butylbenzene, p-xylene, ethylbenzene,1,3,5-trimethylbenzene, m-xylene, toluene, o-xylene, decene, dodecene,tetradecene, and heptadecanal. The solubility parameters of illustrativenonpolar solvents are given in the Table below.

TABLE Solubility Parameters of Illustrative Non-Polar Solventsδ_(Solvent) δ_(Solvent) Non-Polar Solvent (cal/cm³)^(1/2) (kJ/m³)^(1/2)Propane 5.76 373 2,2-Dimethylpropane 6.10 395 Butane 6.58 4262,2-Dimethylbutane 6.69 433 Pentane 7.02 454 Isopropyl Ether 7.06 457Hexane 7.27 470 Triethylamine 7.42 480 Heptane 7.50 485 Octane 7.54 488Nonane 7.64 494 Decane 7.72 499 Isobutyl Isobutyrate 7.74 501Tributylamine 7.76 502 Undecane 7.80 505 2,2,4-Trimethylpentyl Acetate7.93 513 Isobutyl Heptyl Ketone 7.95 514 Diisobutyl Ketone 8.06 521Cyclopentane 8.08 523 Cyclohexane 8.19 530 n-Nonylbenzene 8.49 549n-Octylbenzene 8.56 554 n-Butylbenzene 8.57 554 p-Xylene 8.83 571Ethylbenzene 8.84 572 1,3,5-Trimethylbenzene 8.84 572 m-Xylene 8.88 574Toluene 8.93 578 o-Xylene 9.06 586

The desired products of this invention can be selectively recovered byextraction and phase separation in a polar solvent. As indicated above,the polar solvent can be present with the nonpolar solvent during thereaction or the reaction product fluid can be contacted with a polarsolvent after the reaction. The desired reaction product is preferablyextracted from the reaction product fluid through the use of anappropriate polar solvent such that any extraction of the one or morereactants, metal-organophosphorus ligand complex catalyst, andoptionally free organophosphorus ligand from the reaction product fluidis minimized or eliminated. In an embodiment, the polar solvent is anaqueous mixture preferably containing up to about 8 weight percentwater, more preferably less than about 6 weight percent water, and mostpreferably less than about 4 weight percent water. In this embodiment,the processes of this invention are considered to be essentially“non-aqueous” processes, which is to say, any water present in thereaction mediums is not present in an amount sufficient to cause eitherthe particular reaction or said medium to be considered as encompassinga separate aqueous or water phase or layer in addition to the organicphases. Depending on the particular desired products, suitable polarsolvents include, for example, nitrites, lactones, alkanols, cyclicacetals, pyrrolidones, formamides, sulfoxides and the like. In anotherembodiment, the polar solvent is other than a combination of a primaryalkanol and water.

Mixtures of one or more different polar solvents may be employed ifdesired. The Hildebrand solubility parameter for the polar solvent ormixtures of one or more different polar solvents should be less thanabout 13.5 (cal/cm²)^(½) or 873 (kJ/m³)^(½), preferably less than about13.0 (cal/cm³)^(½) or 841 (kJ/m³)^(½), and more preferably less thanabout 12.5 (cal/cm³)^(½) or 809 (kJ/m³)^(½). The amount of polar solventemployed is not critical to the subject invention and need only be thatamount sufficient to extract the one or more products from the reactionproduct fluid for any given process. In general, the amount of polarsolvent employed may range from about 5 percent by weight up to about 50percent by weight or more based on the total weight of the reactionproduct fluid.

Illustrative polar solvents useful in this invention include, forexample, propionitrile, 1,3-dioxolane, 3-methoxypyropionitrile,N-methylpyrrolidone, N,N-dimethylformamide, 2-methyl-2-oxazoline,adiponitrile, acetonitrile, epsilon caprolactone, glutaronitrile,3-methyl-2-oxazolidinone, water, dimethyl sulfoxide and sulfolane. Thesolubility parameters of illustrative polar solvents are given in theTable below.

TABLE Solubility Parameters of Illustrative Polar Solvents δ_(Solvent)δ_(Solvent) Polar Solvent (cal/cm³)^(1/2) (kJ/m³)^(1/2) Propionitrile10.73 694 1,3-Dioxolane 11.33 733 3-Methoxypropionitrile 11.37 735N-Methylpyrrolidone 11.57 748 N,N-Dimethylformamide 11.76 7612-Methyl-2-Oxazoline 12.00 776 Adiponitrile 12.05 779 Acetonitrile 12.21790 E-Caprolactone 12.66 819 Sulfolane 12.80 828 Glutaronitrile 13.10847 Dimethyl Sulfoxide 13.10 847 3-Methyl-2-Oxazolidinone 13.33 862Water 23.53 1522

Extraction to obtain one phase comprising the one or more reactants,metal-organophosphorus ligand complex catalyst, optionally freeorganophosphorus ligand and nonpolar solvent and at least one otherphase comprising one or, more products and polar solvent is anequilibrium process. The relative volumes of the polar solvent (orextraction solution) and the nonpolar solvent or reaction product fluidin this extraction operation are determined in part by the solubility ofthe one or more reactants, metal-organophosphorus ligand complexcatalyst, optionally free organophosphorus ligand and one or moreproducts in the solvents used, and the amount of desired product to beextracted. For example, when the desired product is extracted, if thedesired product to be extracted shows high solubility in the polarsolvent and is present at a relatively low concentration in the reactionproduct fluid, it is possible to extract the desired product by usingthe polar solvent in a relatively small volume ratio to the reactionproduct fluid. The polar and nonpolar solvents described above may beused as extraction solvents.

Further, as the concentration of the desired product becomes high, it isusually required to increase the ratio of the polar solvent to thereaction product fluid for extracting the desired product from thereaction product fluid. When the desired product shows relatively lowsolubility in the polar solvent, the relative volume of the polarsolvent or extraction solution will have to be increased. Generally, thevolume ratio of the polar solvent or extraction solution to the reactionproduct fluid may be changed within a range of from about 20:1 to about1:20.

In an embodiment, the products produced by the processes of thisinvention may contain sufficient polarity to make the productsimmiscible with the non-polar solvent. Phase separation may occurspontaneously or may be induced by a change in temperature or pressureor the addition of an additive, e.g., salt, or the evaporation of asolvent or combinations thereof. The addition of an external polarsolvent to induce phase separation may not be required for certainprocesses of this invention.

Except as noted above, with respect to the extraction temperature, thereis no merit in employing a temperature higher than the reactiontemperature of the particular process, and desirable results can beobtained by employing an extraction temperature lower than the processreaction temperature. Depending on the particular process, extractiontemperatures may range from about −80° C. or less to about 200° C. orgreater.

The time for mixing the reaction product fluid with the polar solvent,i.e. the time before the phase separation, depends on the rate until thetwo-phases reach the equilibrium condition. Generally, such a time maybevaried from within one minute or less to a longer period of one hour ormore.

The extraction process of this invention is in part an equilibriumprocess of an organophosphorus ligand dissolved in two separate liquidphases. The efficiency of this extraction process can be measured by apartition coefficient Kp1 of the organophosphorus ligand which isdefined as follows: ${Kp1} = \frac{\begin{matrix}\text{Concentration of organophosphorus ligand} \\\text{in the nonpolar phase after extraction}\end{matrix}}{\begin{matrix}\text{Concentration of organophosphorus ligand} \\\text{in the polar phase after extraction}\end{matrix}}$

When the one or more desired products are partitioned between the polarphase and the nonpolar phase by the extraction process of thisinvention, the Kp1 value of the organophosphorus ligand can bemaintained at a level greater than about 5, preferably greater thanabout 7.5, and more preferably greater than about 10, depending on theefficiency of the extraction process. If this Kp1 value is high, theorganophosphorus ligand will preferentially distribute into the nonpolarphase. As used in Kp1, the concentration of organophosphorus ligandincludes both free organophosphorus ligand and organophosphorus ligandcomplexed with the metal.

The extraction process of this invention is also in part an equilibriumprocess of one or more products dissolved in two separate liquid phases.The efficiency of this extraction process can be measured by a partitioncoefficient Kp2 of the one or more products which is defined as follows:${Kp2} = \frac{\begin{matrix}\text{Concentration of products in the} \\\text{nonpolar phase after extraction}\end{matrix}}{\begin{matrix}\text{Concentration of products in the} \\\text{polar phase after extraction}\end{matrix}}$

When the one or more desired products are partitioned between the polarphase and the nonpolar phase by the extraction process of this inventionthe Kp1 value of the products can be maintained at a level less thanabout 2 preferably less than about 1.5 and more preferably less thanabout 1, depending on the efficiency of the extraction process. If thisKp2 value is low, the products will preferentially distribute into thepolar phase.

The extraction process of this invention is further in part anequilibrium process of one or more organophosphorus ligand degradationproducts dissolved in two separate liquid phases. The efficiency of thisextraction process can be measured by a partition coefficient Kp3 of theone or more organophosphorus ligand degradation products which isdefined as follows: ${Kp3} = \frac{\begin{matrix}\text{Concentration of organophosphorus ligand degradation} \\\text{products in the nonpolar phase after extraction}\end{matrix}}{\begin{matrix}\text{Concentration of organophosphorus ligand degradation} \\\text{products~~in the polar phase after extraction}\end{matrix}}$

When the one or more organophosphorus ligand degradation products arepartitioned between the polar phase and the nonpolar phase by theextraction process of this invention the Kp3 value of theorganophosphorus ligand degradation products can be maintained at alevel less than about 2, preferably less than about 1.5, and morepreferably less than about 1, depending on the efficiency of theextraction process. If this Kp3 value is low, the organophosphorusligand degradation products will preferentially distribute into thepolar phase.

The extraction process of this invention is yet further in part anequilibrium process of one or more reaction byproducts dissolved in twoseparate liquid phases. The efficiency of this extraction process can bemeasured by a partition coefficient Kp4 of the one or more reactionbyproducts which is defined as follows: ${Kp4} = \frac{\begin{matrix}\text{Concentration of reaction byproducts in} \\\text{the nonpolar phase after extraction}\end{matrix}}{\begin{matrix}\text{Concentration of reaction byproducts in} \\\text{the polar phase after extraction}\end{matrix}}$

When the one or more reaction byproducts are partitioned between thepolar phase and the nonpolar phase by the extraction process of thisinvention, the Kp4 value of the reaction byproducts can be maintained ata level less than about 2, preferably less than about 1.5, and morepreferably less than about 1, depending on the efficiency of theextraction process. If this Kp4 value is low, the reaction byproductswill preferentially distribute into the polar phase.

The extraction process of this invention is conducted in a manner suchthat three separation criteria are satisfied. The three criteria arereferred to herein as extraction factors and are based on ratios of thepartition coefficients defined above. The relationships embodied by theextraction factors include selectivity of the nonpolar phase for theorganophosphorus ligand with respect to the product, selectivity of thenonpolar phase for the organophosphorus ligand with respect to theorganophosphorus ligand degradation products, and selectivity of thenonpolar phase for the organophosphorus ligand with respect to thereaction byproducts. The three extraction factors ale set out below.

The extraction factor defining selectivity of the nonpolar phase for theorganophosphorus ligand with respect to the one or more products is apartition coefficient ratio as follows: ${Ef1} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp2}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {products}}\end{matrix}}$

The Ef1 value for the above ratio is maintained at a level greater thanabout 2.5, preferably greater than about 3.0, and more preferablygreater than about 3.5, depending on the efficiency of the extractionprocess. If this Ef1 value is high, the extraction selectivity will behigh.

The extraction factor defining selectivity of the nonpolar phase for theorganophosphorus ligand with respect to the one or more organophosphorusligand degradation products is a partition coefficient ratio as follows:${Ef2} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp3}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {organophosphorus}} \\{{ligand}\quad {degradation}\quad {products}}\end{matrix}}$

The Ef2 value for the above ratio is maintained at a level greater thanabout 2.5, preferably greater than about 3.0, and more preferablygreater than about 3.5, depending on the efficiency of the extractionprocess. If this Ef2 value is high, the extraction selectivity will behigh.

The extraction factor defining selectivity of the nonpolar phase for theorganophosphorus ligand with respect to the one or more reactionbyproducts is a partition coefficient ratio as follows:${Ef3} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp4}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {reaction}} \\{{by}{products}}\end{matrix}}$

The Ef3 value for the above ratio is maintained at a level greater thanabout 2.5, preferably greater than about 3.0, and more preferablygreater than about 3.5, depending on the efficiency of the extractionprocess. If this Ef3 value is high, the extraction selectivity will behigh.

The extraction process of this invention may be conducted in one or morestages. The exact number of extraction stages will be governed by thebest compromise between capital costs and achieving high extractionefficiency and ease of operability, as well as the stability of thestarting materials and the desired reaction product to the extractionconditions. Also, the extraction process of this invention may beconducted in a batch or continuous fashion. When conducted continuously,the extraction may be conducted in a cocurrent or countercurrent manneror fractional countercurrent extraction may be used. Suitable fractionalcountercurrent extraction methods are disclosed in copending U.S. patentapplication Ser. Nos. (D-18040 and D-18041), filed on an even dateherewith, the disclosures of which are incorporated herein by reference.In an embodiment, when separating the reaction product fluid, thereaction product fluid preferably contains at least 5 weight percent,preferably at least 10 weight percent, of one or more products.

Illustrative types of extractors that may be employed in this inventioninclude, for example, columns, centrifuges, mixer-settlers, andmiscellaneous devices. Extractors that could be utilized includeunagitated columns, e.g., spray, baffle tray and packed, agitatedcolumns, e.g., pulsed, rotary agitated and reciprocating plate,mixer-settlers, e.g., pump-settler, static mixer-settler and agitatedmixer-settler, centrifugal extractors, e.g., those produced by Robatel,Luwesta, deLaval, Dorr Oliver, Bird and Podbielniak, and miscellaneousextractors, e.g., the emulsion phase contactor and hollow-fibermembrane. A description of these devices can be found in the Handbook ofSolvent Extraction, Krieger Publishing Company, Malabar, Fla., 1991, thedisclosure of which is incorporated herein by reference. As used in thisinvention, the various types of extractors may be combined in anycombination to effect the desired extraction.

Following the extraction, the desired products, along with allyorganophosphorus ligand degradation products and reaction byproducts,may be recovered by phase separation in which the polar phase comprisingone or more products, organophosphorus ligand degradation products andreaction byproducts, is separated from the nonpolar phase. The phaseseparation techniques may correspond to those techniques heretoforeemployed in conventional processes, and can be accomplished in theextractor or in a separated liquid-liquid separation device. Suitableliquid-liquid separation devices include, but are not limited to,coalescers, cyclones and centrifuges. Typical equipment used forliquid-liquid phase separation devices are described in the Handbook ofSeparation process Technology, ISBN 0-471-89558-X, John Wiley & Sons,Inc., 1987, the disclosure of which is incorporated herein be reference.

From a free energy standpoint, to attain dissolution or miscibility of aphosphorous containing ligand in a particular solvent, the enthalpy ofmixing should be as small as possible. The enthalpy of mixing (ΔH_(m))can be approximated by the Hildebrand equation (1)

ΔH _(m)=Φ_(S)Φ_(L) V(δ_(Solvent)−δ_(Ligand))²  (1)

using the solubility parameters of the solvent (δ_(Solvent)) and ligand(δ_(Ligand)), where V is the molar volume of the mixture, and Φ_(S) andΦ_(L) are the volume fractions of the solvent and ligand, respectively.Based on equation (1), the ideal solvent for a ligand would have thesame solubility parameter as the ligand itself, so that ΔH_(m)=0.However. for each ligand there is a characteristic range originatingfrom its solubility parameter which encloses all liquids that aresolvents for the ligand. In general, a solvent or a solvent blend havinga solubility parameter that is within two units of the solubilityparameter of the ligand will dissolve the ligand; however, relativelylarge deviations from this value can sometimes occur, especially ifthere are strong hydrogen bonding interactions. Therefore, equation (2)

δ_(Solvent)−δ_(Ligand)<2.0 (cal/cm³)^(½)  (2)

can be used semi-quantitatively to determine whether a liquid is a goodsolvent for a given ligand. In equation (2), δ_(Solvent) and δ_(Ligand)represent the solubility parameters of the solvent and ligandrespectively.

For purposes of this invention, the solubility parameters for solventscan be calculated from equation (3)

δ_(Solvent)=(ΔH _(v) −RT)d/MW  (3)

in which ΔH_(v) is the heat of vaporization, R is a gas constant, T istemperature in degrees absolute, d is the density of the solvent, and MWis molecular weight of the solvent. The solubility parameters for a widevariety of solvents have been reported by K. L. Hoy, “New Values of theSolubility Parameters from Vapor Pressure Data,” Journal of PaintTechnology, 42, (1970), 76.

The heat of vaporization for phosphorous containing compounds cannot beeasily measured since many of these compounds decompose at highertemperatures. Furthermore, since many phosphorous containing compoundsare solids at room temperature, measurements of density are notconvenient. The solubility parameters, in units of (cal/cm³)^(½), forphosphorus containing ligands can be calculated using equation (4)

δ_(Ligand)=(ΣF _(T)+135.1)/(0.01211+ΣN _(i) V _(1i))1000  (4)

from group contribution theory as developed by (1) K. L. Hoy, “NewValues of the Solubility Parameters from Vapor Pressure Data,” Journalof Paint Technology, 42, (1970), 76, and (2) L. Constantinou, R. Gani,J. P. O'Connell, “Estimation of the Acentric Factor and the Liquid MolarVolume at 298 K Using a New Group Contribution Method,” Fluid PhaseEquilibria, 103, (1995), 1 1. In equation (4), ΣF_(T) is the sum of allthe group molar attraction constants, and Σ_(i)V_(1i) is the sum of allthe first order liquid molar volume constants V_(1i), which occur N_(i)times. These methods have been expanded to include the group molarattraction constant of 79.4 (cal/cm³)^(½)/mole and first order liquidmolar volume constant of 0.0124 m³/kmol for (>P−) derived fromtriphenylphosphine data found in T. E. Daubret, R. P. Danner, H. M.Sibul, and C. C. Stebbins “DIPPR Data Compilation of Pure CompoundProperties,” Project 801, Sponsor Release, July 1995, Design Institutefor Physical Property Data, AIChE, New York, N.Y.

Accordingly illustrative formylester products include, for example,formylundecanoates such as 11-formylundecanoate, 10-formylundecanoate,9-formylundecanoate and the like. Preferred formylesters are representedby the formula

H—C(O)—CH₂—CH₂—(CH₂)₂, —CH₂—C(O)—OR

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving a carbon atom number sufficient to render said formylestermiscible in a polar solvent. Typically, R contains from 1 to about 6 or7 carbon atoms. Illustrative of suitable substituted and unsubstitutedformylester products include those permissible substituted andunsubstituted formylester compounds described in Beilsteins Handbuch derOrganischen Chemie, Springer Verlag KG, 4^(th) Edition, the pertinentportions of which are incorporated herein by reference.

Preferred formylester products include formylundecanoates and/orderivatives thereof. As used herein, derivatives of formylestersinclude, for example, formylacids and salts of formylacids. Thisinvention is not intended to be limited in any manner by the permissiblederivatives of formylesters.

In another embodiment, this invention includes batchwise or continuouslygenerated reaction mixtures comprising:

(1) one or more substituted or unsubstituted formylesters and/orderivatives thereof;

(2) optionally one or more substituted or unsubstituted unsaturatedesters and/or derivatives thereof; and

(3) optionally castor oil and/or derivatives thereof;

wherein the weight ratio of component (1) to the sum of components (2)and (3) is greater than about 0.1; and the weight ratio of component (3)to the sum of components (1) and (2) is about 0 to about 100. Also, thisinvention includes reaction mixtures comprising one or more formylestersand/or derivatives thereof in which the reaction mixtures are preparedby the processes described herein. In accordance with this invention,the formylester product mixtures may be extracted and separated from theother components of the crude reaction mixtures in which the formylestermixtures are produced by phase separation as described above.

The formylesters produced by the processes of this invention can undergofurther reaction(s) to afford desired derivatives thereof. Suchpermissible derivatization reactions can be carried out in accordancewith conventional procedures known in the art. Illustrativederivatization reactions include, for example, hydrogenation,esterification, etherification, animation, alkylation, dehydrogenation,reduction, acylation, condensation, carboxylation, carbonylation,oxidation, cyclization, silylation and the like, including permissiblecombinations thereof. This invention is not intended to be limited inany manner by the permissible derivatization reactions of formylesters.

It is generally preferred to carry out the hydroformylation processes ofthis invention in a continuous manner. In general, continuoushydroformylation processes are well known in the art and may involve:(a) hydroformylating the olefinic starting material(s) with carbonmonoxide and hydrogen in a liquid homogeneous reaction mixturecomprising a nonpolar solvent, the metal-organophosphorus ligand complexcatalyst, free organophosphorus ligand, and optionally a polar solvent;(b) maintaining reaction temperature and pressure conditions favorableto the hydroformylation of the olefinic starting material(s); (c)supplying make-up quantities of the olefinic starting material(s),carbon monoxide and hydrogen to the reaction medium as those reactantsare used up; (d) mixing at least a portion of the reaction medium with apolar solvent to extract the desired aldehyde hydroformylationproduct(s) from the reaction medium; and (e) recovering the desiredaldehyde product(s) by phase separation.

At the conclusion of (or during) the process of this invention, thedesired formylesters may be recovered from the reaction mixtures used inthe process of this invention. For instance, in a continuous liquidcatalyst recycle process the portion of the liquid reaction mixture(containing formylester product, catalyst, etc.) removed from thereaction zone can be passed to a separation zone wherein the desiredformylester product can be extracted and separated via phase separationfrom the liquid reaction mixture, and further purified if desired. Theremaining catalyst containing liquid reaction mixture may then berecycled back to the reaction zone as may if desired any othermaterials, e.g., unreacted olefin, together with any hydrogen and carbonmonoxide dissolved in the liquid reaction after separation thereof fromthe formylester product. Following phase separation in which a layer ofthe extraction fluid, e.g., polar solvent and one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and one or more formylesters, is separated from a layer ofthe remaining reaction product fluid, the desired formylesters can thenbe separated from the undesired organophosphorus ligand degradationproducts and reaction byproducts by conventional methods such asdistillation.

Hydrogenation Step or Stage

The hydrogenation processes involve converting one or more substitutedor unsubstituted formylesters, e.g., 11-formylundecanoate, to one ormore substituted or unsubstituted ester alcohols, e.g.,12-hydroxydodecanoate, or to one or more substituted or unsubstituteddiols, e.g., 1,12-dodecanediols, in one or more steps or stages. As usedherein, the term “hydrogenation” is contemplated to include, but is notlimited to, all permissible hydrogenation processes which involveconverting one or more substituted or unsubstituted formylesters, e.g.,formylundecanoates, to one or more substituted or unsubstituted esteralcohols, e.g., hydroxydodecanoates, or to one or more substituted orunsubstituted diols, e.g., dodecanediols. In general, the hydrogenationstep or stage comprises reacting one or more substituted orunsubstituted formylesters in the presence of a hydrogenation catalystto produce one or more substituted or unsubstituted ester alcohols orone or more substituted or unsubstituted diols.

Formylundecanoates useful in the hydrogenation processes are knownmaterials and can be prepared by the hydroformylation steps describedabove or by other conventional processes. Reaction mixtures comprisingformylundecanoates may be useful herein. The amounts offormylundecanoates employed in the hydrogenation step is not narrowlycritical and can be any amount sufficient to produce hydroxydodecanoatesand/or dodecanediols, preferably in high selectivities. Theformylundecanoates may be fed to the reactor in any convenient manner,such as in solution, or as a neat liquid.

The hydrogenation process may be carried out in one or more steps orstages and in any permissible sequence of steps or stages. In a one stepprocess, hydroxydodecanoate and/or dodecanediols are the desiredproducts leaving the reaction zone. In a multistep or multistageprocess, intermediate products are the major products leaving theindividual reaction zones.

The particular hydrogenation reaction conditions are not narrowlycritical and can be any effective hydrogenation conditions sufficient toproduce the hydroxydodecanoates and/or dodecanediols. The reactors maybe stirred tanks, tubular reactors and the like. The exact reactionconditions will be governed by the best compromise between achievinghigh catalyst selectivity, activity, lifetime and ease of operability aswell as the intrinsic reactivity of the formylundecanoates in questionand the stability of the formylundecanoates and the desired reactionproduct to the reaction conditions. Illustrative of certain reactionconditions that may be employed in the hydrogenation processes aredescribed, for example, in P. N. Rylander, Hydrogenation Methods,Academic Press. New York, 1985, Chapter 5, the disclosure of which isincorporated herein by reference. Products may be recovered after aparticular reaction zone and purified if desired although they may beintroduced to the next reaction zone without purification. Recovery andpurification may be by any appropriate means, which will largely bedetermined by the particular reactants employed.

The hydrogenation reaction can be conducted at a temperature of fromabout 0° C. to about 400° C. for a period of about 1 minute or less toabout 4 hours or longer with the longer time being used at the lowertemperature, preferably from about 50° C. to about 300° C. for about 1minute or less to about 2 hours or longer, and more preferably at about50° C. to about 25° C. for about 3 hours or less. The temperature shouldbe sufficient for reaction to occur (which may vary with catalystsystem) but not so high as to cause formylundecanoate decomposition orpolymerization.

The hydrogenation reaction can be conducted over a wide range ofpressures ranging from about 10 psig to about 4500 psig. It ispreferable to conduct the hydrogenation reaction at pressures of fromabout 100 psig to about 2000 psig. The hydrogenation reaction ispreferably effected in the liquid or vapor states or mixtures thereof.The total pressure will depend on the catalyst system used. The hydrogenpartial pressure should be chosen to maximize the efficiency of thehydrogenation catalyst and obtain the desired selectivity and degree ofconversion.

The hydrogenation reaction step or stage involve the use of a catalyst.Such catalysts are known in the art and can be used in conventionalamounts. Of course mixtures of catalysts can also be employed ifdesired. The amount of catalyst employed will be dependent on thehydrogenation reaction conditions employed and the amount should besufficient to obtain the desired selectivity and degree of conversion.In general, the amount of catalyst employed should be sufficient toenable a conversion of formylundecanoates to hydroxydodecanoates and/ordodecanediols of at least about 5 percent, preferably at least about 20percent, and more preferably at least about 50 percent.

As indicated above, the substituted and unsubstitutedhydroxydodecanoates and/or dodecanediols produced by the hydrogenationstep can be separated by conventional techniques such as filtration,distillation, extraction, precipitation, crystallization, membraneseparation or other suitable means. For example, a crude reactionproduct can be subjected to a distillation-separation at atmospheric orreduced pressure through a packed distillation column. Reactivedistillation may be useful in conducting the hydrogenation reactionstep.

Illustrative substituted and unsubstituted hydroxydodecanoates that canbe prepared by the hydrogenation stage or step of this invention includeone or more of the following: methyl 12-hydroxydodecanoate, ethyl12-hydroxydodecanoate, propyl 12-hydroxydodecanoate, and butyl12-hydroxydodecanoate, including mixtures comprising one or more of theabove ester alcohols. Preferred ester alcohols are represented by theformula

RO(O)C—CH₂—CH₂—(CH₂)₇—CH₂—CH₂—OH

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving from 1 to about 6 or 7 carbon atoms. Illustrative of suitablesubstituted and unsubstituted ester alcohols include those permissiblesubstituted and unsubstituted ester alcohols which are described inDictionary of Organic Compounds, Sixth Edition, Chapman and Hall,Cambridge, 1996, the pertinent portions of which are incorporated hereinby reference.

Illustrative substituted and unsubstituted diols that can be prepared bythe hydrolysis stage or step of this invention include one or more ofthe following: 1,12-dodecanediol, 2-methyl-1,11-undecanediol,3-methyl-1,11-undecanediol, including mixtures comprising one or more ofthe above diols. Preferred diols are represented by the formula

HO—CH₂—CH₂—CH₂—(CH₂)₇—CH₂—CH₂—OH

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving from 1 to about 6 or 7 carbon atoms. Illustrative of suitablesubstituted and unsubstituted diols include those permissiblesubstituted and unsubstituted diols which are described in Dictionary ofOrganic Compounds, Sixth Edition, Chapman and Hall, Cambridge, 1996, thepertinent portions of which are incorporated herein by reference.

The hydroxydodecanoates and dodecanediols described herein are useful ina variety of applications, such as the manufacture of synthetic fibers,plastics, bristles, film, coatings, synthetic leather, plasticizers andpaint vehicles, crosslinking agent for polyurethanes, and the like. Thehydroxydodecanoates call be reacted with polyols, such as diethyleneglycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol,trimethylolpropane, and the like, to give polyester polyols which canimprove the flexibility and the hydrolytic resistance of coatings. Thepolyester polyols can be reacted with diisocyanates in the preparationof urethane elastomers. Self condensation of the ester alcohol can leadto a thermoplastic polyester with a low solubility parameter. Hydrolysisof the ester alcohol to the acid alcohol can lead to a crosslinkerhaving dual reactivity for liquid coatings and powder coatings as wellas adhesives.

Reductive Amination Step or Stage

The reductive Amination processes involve converting one or moresubstituted or unsubstituted formylesters. e.g., 11-formylundecanoate,to one or more substituted or unsubstituted aminoesters, e.g.,12-aminododecanoate, in one or more steps or stages. As used herein, theterm “reductive amination” is contemplated to include, but is notlimited to, all permissible reductive amination processes which involveconverting one or more substituted or unsubstituted formylesters, e.g.,formylundecanoates, to one or more substituted or unsubstitutedaminoesters, e.g., aminododecanoate. In general, the reductive aminationstep or stage comprises reacting one or more substituted orunsubstituted formylesters optionally in the presence of a reductiveamination catalyst to produce one or more substituted or unsubstitutedaminoesters.

Formylundecanoates useful in the reductive amination processes are knownmaterials and can be prepared by the hydroformylation steps describedabove or by other conventional processes. Reaction mixtures comprisingformylundecanoates may be useful herein. The amounts offormylundecanoates employed in the reductive amination stop is notnarrowly critical and can be any amount sufficient to produceaminododecanoates, preferably in high selectivities.

The reductive amination process may be carried out in one or more stepsor stages and in any permissible sequence of steps or stages. In a onestep process, aminododecanoate is the desired product leaving thereaction zone. In a multistep or multistage process, intermediateproducts are the major products leaving the individual reaction zones.

The particular reductive amination reaction conditions are not narrowlycritical and can be any effective reductive amination condition issufficient to produce the aminododecanoates. The reactors may be stirredtanks, tubular reactors and the like. The exact reaction conditions willbe governed by the best compromise between achieving high catalystselectivity, activity, lifetime and ease of operability, as well as theintrinsic reactivity of the formylundecanoates in question and thestability of the formylundecanoates and the desired reaction product tothe reaction conditions. Illustrative of certain reaction conditionsthat may be employed in the reductive amination processes are described,for example, in U.S. Pat. Nos. 2,777,873, 4,766,237, 5,068,398 and5,700,934, the disclosures of which are incorporated herein byreference. Products may be recovered after a particular reaction zoneand purified if desired although they may be introduced to the nextreaction zone without purification. Recovery and purification may be byany appropriate means, which will largely be determined by theparticular reactants employed.

The reductive amination reaction can be conducted at a temperature offrom about 0° C. to about 400° C. for a period of about 1 minute or lessto about 4 hours or longer with the longer time being used at the lowertemperature, preferably from about 50° C. to about 300° C. for about 1minute or less to about 2 hours or longer, and more preferably at about50° C. to about 250° C. for about 1 minute or less to about 2 hours orlonger. The temperature should be sufficient for reaction to occur(which may vary with catalyst system) but not so high as to causeformylundecanoate decomposition or polymerization.

The reductive amination reaction can be conducted over a wide range ofpressures ranging from about 10 psig to about 4500 psig. It ispreferable to conduct the reductive amination reaction at pressures offrom about 100 psig to about 2000 psig. The reductive amination reactionis preferably effected in the liquid or vapor states or mixturesthereof. The total pressure will depend on the catalyst system used. Thehydrogen partial pressure should be chosen to maximize the lifetime ofthe amination catalyst and obtain the desired selectivity and degree ofconversion.

Ammonia is preferably employed as the aminating agent in these reactionsin conventional amounts, preferably in excess amounts, and it may be fedto the reactor in a variety of ways, including as a liquid, and a gas,in solution in for example water, or as ammonium salts in solution or insome other appropriate manner, e.g., urea. Any excess ammonia ispreferably separated off after reductive amination is completed. Theformylundecanoates may be fed to the reactor in any convenient manner,such as in solution, or as a neat liquid.

Some of the reaction steps or stages may involve the use of a catalyst.Such catalysts are known in the art and can be used in conventionalamounts. Catalysts useful in the reductive amination stage or stepinclude, for example, Raney nickel, Raney cobalt, nickel onsilica/alumina, palladium on carbon, platinum on carbon, rhodium onalumina, and the like. Of course mixtures of catalysts can also beemployed if desired. The amount of catalyst employed will be dependenton the reductive amination reaction conditions employed and the amountshould be sufficient to obtain the desired selectivity and degree ofconversion. In general, the amount of catalyst employed should besufficient to enable a conversion of formylundecanoates toaminododecanoate of at least about 5 percent, preferably at least about20 percent, and more preferably at least about 50 percent.

As indicated above, the substituted and unsubstituted aminododecanoatesproduced by the reductive amination step can be separated byconventional techniques such as filtration, distillation, extraction,precipitation, crystallization, membrane separation or other suitablemeans. For example, a crude reaction product can be subjected to adistillation-separation at atmospheric or reduced pressure through apacked distillation column. Reactive distillation may be useful inconducting the reductive amination reaction step.

Illustrative aminododecanoates that can be prepared by the processes ofthis invention include, for example, 12-aminododecanoate, methyl12-aminododecanoate, ethyl 12-aminododecanoate, propyl12-aminododecanoate, and butyl 12-aminododecanoate. Preferredaminoesters are represented by the formula

H₂N—CH₂—CH₂—CH₂—(CH₂)₇—CH₂—C(O)—OR

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving from 1 to about 6 or 7 carbon atoms. Illustrative of suitablesubstituted and unsubstituted aminododecanoates include thosepermissible substituted and unsubstituted aminododecanoates which aredescribed in Dictionary of Organic Compounds, Sixth Edition, Chapman andHall, Cambridge, 1996, the pertinent portions of which are incorporatedherein by reference.

Oxidation Stage or Step

The oxidation stare or step of this invention involves converting one ormore substituted or unsubstituted formylesters, e.g.,11-formylundecanoate, to one or more substituted or unsubstitutedacidoesters, e.g., monoalkyl ester of 1,12-dodecanedioic acid. Theoxidation stage or step of this invention may be conducted in one ormore steps or stages, preferably a one step process.

As used herein, the term “oxidation” is contemplated to include allpermissible oxidation processes which involve converting one or moresubstituted or unsubstituted formylesters, e.g., formylundecanoates, toone or more substituted or unsubstituted acidoesters, e.g., monoalkylesters of dodecanedioic acid. In general, the oxidation step or stagecomprises reacting one or more substituted or unsubstitutedformylesters, e.g., 11-formylundecanoate, with an oxygen source, e.g.,air, essentially pure oxygen or oxygen-enriched air containing at leastabout 50% oxygen, optionally in the presence of an oxidation catalyst oran oxidation catalyst and a promoter, and optionally an initiator, toproduce one or more substituted or unsubstituted acidoesters, e.g.,monoalkyl esters of dodecanedioic acid.

Formylundecanoates useful in the oxidation process are described aboveand can be prepared by the methods described above. The amount offormylundecanoates employed in the oxidation step is not narrowlycritical and can be any amount sufficient to produce monoalkyl esters ofdodecanedioic acid, preferably in high selectivities.

The oxidation process may be carried out in one or more steps or stagesand in any permissible sequence of steps or stages. In a one stepprocess, monoalkyl esters of dodecanedioic acid are the desired productsleaving the reaction zone. In a multistep or multistage process,intermediate products are the major products leaving the individualreaction zones. Of course some overlap of individual transformations mayoccur, so that in a two stage process, some transformations may occur indifferent order.

The particular oxidation reaction conditions are not narrowly criticaland can be any effective oxidation conditions sufficient to producemonoalkyl esters of dodecanedioic acid. The reactors may be stirredtanks, tubular reactors and the like. The exact reaction conditions willbe governed by the best compromise between achieving high selectivity,activity, lifetime and ease of operability, as well as the intrinsicreactivity of the formylundecanoates in question and the stability ofthe formylundecanoates to the reaction conditions. Illustrative ofcertain reaction conditions that may be employed in the oxidationprocesses are described, for example, in U.S. Pat. Nos. 8,331,121,5,840,959, 4,537,987 and 5,817,870, the disclosures of which areincorporated herein by reference. Products may be recovered after aparticular reaction zone and purified if desired although they may beintroduced to the next reaction zone without purification. Recovery andpurification may be by any appropriate means, which will largely bedetermined by the particular formylundecanoate starting materialemployed.

The oxidation reaction can be conducted at a temperature of from about0° C. to about 200° C. for a period of about 1 minute or less to about 4hours or longer with the longer time being used at the lowertemperature, preferably from about 10° C. to about 150° C. for about 1minute or less to about 2 hours or longer, and more preferably at about20° C. to about 125° C. for about 1 minute or less to about 2 hours orlonger. The temperature should be sufficient for reaction to occur(which may vary with catalyst system) but not so high as to causeformylundecanoate decomposition.

The oxidation reaction can be conducted over a wide range of pressuresranging from about 10 psig to about 2000 psig. It is preferable toconduct the oxidation reaction at pressures of from about 10 psig toabout 1000 psig. The oxidation reaction is preferably effected in theliquid or vapor states or mixtures thereof. The total pressure willdepend on the temperature and other reaction conditions.

The oxidation reaction can be conducted using a variety of oxidants.Illustrative oxidants include, for example, molecular oxygen, molecularoxygen mixed with an inert gas such as nitrogen, molecular oxygen inair, hydrogen peroxide, peracetic acid and the like. The oxidant can beemployed in conventional amounts.

The oxidation step or stage may involve the use of a catalyst. Suchcatalysts are known in the art and can be homogeneous or heterogeneous.Catalysts useful in the oxidation stage or step include, for example,palladium supported on carbon, palladium on supports such as alumina orsilica, platinum on carbon, alkali metal hydroxide, cobalt acetate,manganese acetate, bismuth molybdates, molybdenum-vanadium oxides,manganese porphyrin complexes, homogeneous molybdenum complexes, and thelike. Of course mixtures of oxidation catalysts can also be employed ifdesired. The amount of catalyst employed will be dependent on theoxidation reaction conditions employed and the amount should besufficient to obtain the desired selectivity and degree of conversion.In general, the amount of catalyst employed should be sufficient toenable a conversion of formylundecanoate to monoalkyl ester ofdodecanedioic acid of at least about 5 percent, preferably at leastabout 20 percent, and more preferably at least about 50 percent.

The oxidation process may also be conducted in the presence of apromoter. As used herein, the term “promoter”, when used in the contextof oxidation, means a material added to the oxidation reaction mixtureto impart a promotion effect to catalytic activity, e.g., rate, productselectivity, and/or catalyst stability (mechanical or dimensionalstrength of the catalyst). Illustrative promoters include, for example,alkali metal hydroxide, acetate salts, Group VII metals, rare earthoxides, alkaline earth metals, and the like. The promoter may be presentin the oxidation reaction mixture either alone or incorporated into thecatalyst structure. The desired promoter will depend on the nature ofthe catalysts. The concentration of the promoter employed will dependupon the details of the catalyst system employed.

The oxidation process may also be conducted in the presence of aninitiator. As used herein, the term “initiator”, when used in thecontext of oxidation, means a material added to the oxidation reactionmixture to initiate the reaction by starting, for example, a freeradical chain reaction. Illustrative initiators include, for example,sodium persulfate, ammonium persulfate, benzoyl peroxide, perbenzoicacid, tertiary-butyl hydroperoxide, alkyl peroxide, peracids, peresters,azobisisobutyronitrile, redox systems such as hydrogen peroxide/ironacetate, and the like. The initiator may be present in the oxidationreaction mixture either alone or in addition to a catalyst. The desiredinitiator will depend on the nature of the reaction system and reactionconditions. The concentration of the initiator employed will depend uponthe details of the reaction system employed.

Illustrative substituted and unsubstituted monoalkyl esters ofdodecanedioic acid that can be prepared by the oxidation stage or stepof this invention include one or more of the following: monoalkyl esterof 1,12-dodecanedioic acid, methyl ester of 1,12-dodecanedioic acid,ethyl ester of 1,12-dodecanedioic acid, propyl ester of1,12-dodecanedioic acid, and butyl ester of 1,12-dodecanedioic acid,including mixtures comprising one or more of the above monoalkyl estersof dodecanedioic acid. Preferred acidoesters are represented by theformula

HO(O)C—CH₂—CH₂—(CH₂)₇—CH₂—C(O)—OR

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving from 1 to about 6 or 7 carbon atoms. Illustrative of suitablesubstituted and unsubstituted monoalkyl esters of dodecanedioic acidinclude those permissible substituted and unsubstituted monoalkyl estersof dodecanedioic acid which are described in Dictionary of OrganicCompounds, Sixth Edition, Chapman and Hall, Cambridge. 1996, thepertinent portions of which are incorporated herein by reference.

Recovery and purification of monoalkyl esters of dodecanedioic acid maybe by any appropriate means, and may include phase separation,extraction, precipitation, absorption, crystallization, membraneseparation, derivative formation and other suitable means. Distillationmay result in decomposition at atmospheric pressure and is thereforeundesirable. Crystallization is a preferred purification method. Thesubsequent derivatization of the monoalkyl ester of dodecanedioic acidmay be conducted without the need to separate the monoalkyl ester ofdodecanedioic acid from the other components of the crude reactionmixtures.

In an embodiment, the oxidation stage or step of this invention may becarried out in a liquid oxidation reactor such as described, forexample, in copending U.S. patent application Ser. No. 09/063,675, filedon Apr. 21, 1998, the disclosure of which is incorporated herein byreference.

Hydrolysis Step or Stave

The hydrolysis process involves converting (when reductive amination isemployed) one or more substituted or unsubstituted aminoesters, e.g.,12-aminododecanoate, to one or more substituted or unsubstitutedaminoacids, e.g., 12-aminododecanoic acid, in one or more steps or,stages, or converting (when oxidation is employed) one or moresubstituted or unsubstituted acidoesters, e.g., monoalkyl ester of1,12-dodecanedioic acid, to one or more substituted or unsubstituteddiacids, e.g., 1,12-dodecanedioic acid, in one or more steps or stages.As used herein, the term “hydrolysis” is contemplated to include, but isnot limited to, all permissible hydrolysis processes which involveconverting one or more substituted or unsubstituted aminoesters to oneor more substituted or unsubstituted aminoacids or which involveconverting one or more substituted or unsubstituted acidoesters to oneor more substituted or unsubstituted diacids. In general, the hydrolysisstep or stage comprises reacting one or more substituted orunsubstituted aminoesters, e.g., aminododecanoates, optionally in thepresence of a catalyst to produce one or more substituted orunsubstituted aminoacids, e.g., aminododecanoic acids, or reacting oneor more substituted or unsubstituted acidoesters, e.g., monoalkyl estersof dodecanedioic acid, optionally in the presence of a catalyst toproduce one or more substituted or unsubstituted diacids, e.g.,dodecanedioic acids.

Aminododecanoates useful in the hydrolysis process are known materialsand can be prepared by the reductive amination step described above orby other conventional processes. Reaction mixtures comprisingaminododecanoates may be useful herein. Monoalkyl esters ofdodecanedioic acid useful in the hydrolysis process are known materialsand can be prepared by the oxidation step described above or by otherconventional processes. Reaction mixtures comprising monoalkyl esters ofdodecanedioic acid may be useful herein. The amounts ofaminododecanoates and monoalkyl esters of dodecanedioic acid employed inthe hydrolysis step are not narrowly critical and can be any amountssufficient to produce either aminododecanoic acids or dodecanedioicacids, preferably in high selectivities.

The hydrolysis process may be carried out in one or more steps or stagesand in any permissible sequence of steps or stages. In a one stepprocess, aminododecanoic acids or dodecanedioic acids are the desiredproducts leaving the reaction zone. In a multistep or multistageprocess, intermediate products are the major products leaving theindividual reaction zones.

The particular hydrolysis reaction conditions are not narrowly criticaland can be any effective hydrolysis conditions sufficient to produceeither aminododecanoic acids or dodecanedioic acids. The reactors may bestirred tanks, tubular reactors and the like. The exact reactionconditions will be governed by the best compromise between achievinghigh catalyst selectivity, activity, lifetime and ease of operability,as well as the intrinsic reactivity of the aminododecanoates ormonoalkyl esters of dodecanedioic acid in question and the stability ofthe aminododecanoates or monoalkyl esters of dodecanedioic acid and thedesired reaction product to the reaction conditions. Illustrative ofcertain reaction conditions that may be employed in the hydrolysisprocess are described, for example, in U.S. Pat. No. 4,950,429, thedisclosure of which is incorporated herein by reference. Products may berecovered after a particular reaction zone and purified if desiredalthough they may be introduced to the next reaction Zone withoutpurification. Recovery and purification may be by any appropriate means,which will largely be determined by the particular reactants employed.

The hydrolysis reaction can be conducted at a temperature of from about0° C. to about 400° C. for a period of about 1 minute or less to about 4hours or longer with the longer time being used at the lowertemperature, preferably from about 50° C. to about. 300° C. for about 1minute or less to about 2 hours or longer, and more preferably at about50° C. to about 250° C. for about 1 minute or less to about 2 hours orlonger. The temperature should be sufficient for reaction to occur(which may vary with catalyst system) but not so high as to causeaminododecanoate or monoalkyl ester of dodecanedioic acid decomposition.

The hydrolysis reaction can be conducted over a wide range of pressuresranging from about 10 psig to about 4500 psig. It is preferable toconduct the hydrolysis reaction at pressures of from about 10 psig toabout 2000 psig. The hydrolysis reaction is preferably effected in theliquid or vapor states or mixtures thereof. The total pressure willdepend on the catalyst system used.

Some of the reaction steps or stages may involve the use of a catalyst.Such catalysts ale known in the art and can be homogeneous orheterogeneous. Catalysts useful in the hydrolysis stage or step areknown materials and include, for example, Group IVB metal oxides,metallic phosphates which may or may not have a cyclic structure,metallic polyphosphates which may or may not have a condensed structure,Group VIB metal containing substances, and the like. Typical esterhydrolysis catalysts include acids and acid resins. See, for example, inU.S. Pat. No. 4,950,429, supra. Of course mixtures of hydrolysiscatalysts can also be employed if desired. The amount of catalystemployed will be dependent on the hydrolysis reaction conditionsemployed and the amount should be sufficient to obtain the desiredselectivity and degree of conversion. In general, the amount of catalystemployed should be sufficient to enable a conversion to aminododecanoicacid or dodecanedioic acid of at least about 5 percent, preferably atleast about 20 percent, and more preferably at least about 50 percent.

As indicated above, the substituted and unsubstituted aminododecanoicacids or dodecanedioic acids produced by the hydrolysis step can beseparated by conventional techniques such as distillation, extraction,precipitation, crystallization, membrane separation or other suitablemeans. For example, a crude reaction product can be subjected to adistillation-separation at atmospheric or reduced pressure through apacked distillation column. Reactive distillation may be useful inconducting the hydrolysis reaction step. Illustrative epsiloncaprolactams that can be prepared by the processes of this invention aredescribed above.

Illustrative substituted and unsubstituted aminododecanoic acids thatcan be prepared by the hydrolysis stage or step of this inventioninclude one or more of the following: 12-aminododecanedioic acid,11-amino-10-methylundecanedioic acid, including mixtures comprising oneor more of the above aminoacids. Preferred aminoacids are represented bythe formula

HO(O)C—CH₂—CH₂—(CH₂)₇—CH₂—CH₂—NH₂

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving from 1 to about 6 or 7 carbon atoms. Illustrative of suitablesubstituted and unsubstituted aminoacids include those permissiblesubstituted and unsubstituted aminoacids which are described inDictionary of Organic Compounds, Sixth Edition, Chapman and Hall,Cambridge, 1996, the pertinent portions of which are incorporated hereinby reference.

Illustrative substituted and unsubstituted dodecanedioic acids that canbe prepared by the hydrolysis stage or step of this invention includeone or more of the following: 1,12-dodecanedioic acid,2-methyl-1,11-undecanedioic acid, including mixtures comprising one ormore of the above diacids. Preferred diacids are represented by theformula

HO(O)C—CH₂—CH₂—(CH₂)₇—CR₂—C(O)—OH

wherein R is hydrogen or a substituted or unsubstituted hydrocarbonhaving from 1 to about 6 or 7 carbon atoms. Illustrative of suitablesubstituted and unsubstituted diacids include those permissiblesubstituted and unsubstituted diacids which are described in Dictionaryof Organic Compounds, Sixth Edition, Chapman and Hall, Cambridge, 1996,the pertinent portions of which are incorporated herein by reference.

The aminododecanoic acids and dodecanedioic acids described herein areuseful in a variety of applications, such as the manufacture ofsynthetic fibers (especially nylon 12 from polymerization of12-aminododecanoic acid and nylon 6,12 from copolymerization of1,12-dodecanedioic acid and hexamethylenediamine), plastics, bristles,film, coatings, synthetic leather, plasticizers and paint vehicles,crosslinking agent for polyurethanes, and the like. The manufacture ofpolyamides is a preferred application.

The processes of this invention can be conducted in a batch orcontinuous fashion, with recycle of unconsumed starting materials ifrequired. The reaction can be conducted in a plurality of reactionzones, in series or in parallel or it may be conducted batchwise orcontinuously in an elongated tubular zone or series of such zones. Forexample, a backmixed reactor may be employed in series with amultistaged reactor with the backmixed reactor being first. Thematerials of construction employed should be inert to the startingmaterials during the reaction and the fabrication of the equipmentshould be able to withstand the reaction temperatures and pressures.Means to introduce and/or adjust the quantity of starting materials oringredients introduced batchwise or continuously into the reaction zoneduring the course of the reaction can be conveniently utilized in theprocesses especially to maintain the desired molar ratio of the startingmaterials. The reaction steps may be effected by the incrementaladdition of one of the starting materials to the other. Also, thereaction steps can be combined by the joint addition of the startingmaterials. When complete conversion is not desired or not obtainable,the starting materials can be separated from the product by phaseseparation, and the starting materials then recycled back into thereaction zone.

The processes may be conducted in either glass lined, stainless steel orsimilar type reaction equipment. The reaction zone may be fitted withone or more internal and/or external heat exchanger(s) in order tocontrol undue temperature fluctuations, or to prevent any possible“runaway” reaction temperatures.

The processes of this invention may be conducted in one or more reactionsteps and more than one reactive stages. The exact number of reactionsteps and reactive stages will be governed by the best compromisebetween capital costs and achieving high catalyst selectivity, activity,lifetime and ease of operability, as well as the intrinsic reactivity ofthe starting materials in question and the stability of the startingmaterials and the desired reaction product to the reaction conditions.

For purposes of this invention, the term “hydrocarbon” is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. Such permissible compounds may also have one or moreheteroatoms. In a broad aspect, the permissible hydrocarbons includeacyclic (with or without heteroatoms) and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticorganic compounds which can be substituted or unsubstituted.

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

Certain of the following examples are provided to further illustratethis invention. It is to be understood that all manipulations werecarried out under a nitrogen atmosphere unless otherwise stated. Also,all examples were carried out at ambient temperature unless otherwisestated.

The ligands set out below are used in the following examples.

EXAMPLE 1

To a magnetically stirred 100 milliliter stainless steel autoclave undernitrogen was charged 20 milliliters of a solution containing 572 partsper million of rhodium(acetylacetonato)dicarbonylrhodium(I), and 0.63weight percent of Ligand A in heptane.

The mixture was then heated to 70° C. and the pressure allowed to reachequilibrium. To this mixture was then added 1.0 milliliter of ethyl10-undecenoate. The reactor was then sealed. The reactor was then placedunder H₂:CO and held at a pressure between 95 and 100 psig for 5 hours.At this point, the contents of the reactor were discharged into anitrogen purged vessel. Analysis of the discharged solution indicated(96% conversion of the ethyl 10-undecenoate. In addition, normal tobranched ratio, defined as the amount of normal or straight chainisomer/amount of branched isomers, for the aldehyde product was 42.

EXAMPLE 2

At room temperature, 10 milliliters of the discharged reaction solutionfrom Example 1 was transferred to a nitrogen purged vessel. To thevessel was then added an equal volume of acetonitrile. The mixture wasvigorously shaken for several minutes then allowed to settle and phaseseparate. The layers were then analyzed for rhodium content andhydroformylation product. The partition coefficient of the catalyst andthe product, as defined bay Kpartition=amount of material in the heptanephase/amount of material in the acetonitrile phase, was then determinedfor each component. Kpartition for rhodium was found to be 170, andKpartition for the hydroformylation product was found to be 0.25.

The extraction factor of the catalyst for one phase relative to theproduct, as defined by extraction factor=Kpartition rhodium/Kpartitionproduct, was 680.

EXAMPLE 3

A solution of rhodium dicarbonyl acetylacetonate (10.1 milligrams; 0.039mmol) and Ligand B (98.1 milligrams; 0.117 mmol) in heptane (18 grams)was placed in a Parr reactor and activated for about 1 hour at 70° C.and 100 psi of syngas (CO/H₂ 1:1). Ethyl 10-undecenoate (1.2 grams) andoctane (0.8 grams, internal standard) were charged to the autoclave andhydroformylated at 70° C. and 100 psi of syngas. The CO/H₂ ratio wasmaintained 1:1 during the course of reaction. After 20 hours thereaction mixture was analyzed by gas chromatography. The startingmaterial was completely consumed and selectivity to the aldehydeproducts was 92% with the n/i ratio of 43.

EXAMPLE 4

The autoclave containing the hydroformylation mixture from Example 3 wascooled to ambient temperature and its contents were discharged to give aone phase system. A portion of the reaction solution (2 milliliters) wasextracted with acetonitrile (2 milliliters). The phases were separatedand the content of ethyl 11-formylundecanoate product was determined inboth phases by gas chromatography. The partition coefficient of theproduct, as defined by Kpartition=amount of product in the heptanephase/amount of product in the acetonitrile phase, was determined to be0.25.

EXAMPLE 5

A solution of rhodium dicarbonyl acetylacetonate (10.1 mg; 0.039 mmol)and Ligand B (98.1 mg; 0.117 mmol) in heptane (18 g) was placed in a 80ml Parr reactor and activated for about 1 hour at 70° C. and 100 psi ofsyngas (CO/H₂1:1). Methyl 10-undecenoate (1.2 g; 6.06 mmol) and octane(0.8 g, internal standard) were charged to the autoclave.Hydroformylation was carried out at 70° C. and 100 psi of syngas withthe CO/H₂ ratio of 1:1. The reaction mixture was monitored by gaschromatography. After 20 hours, the starting material was completelyconsumed and selectivity to the aldehyde products was 80% with n/isoratio of 33.

EXAMPLE 6

The autoclave containing the hydroformylation mixture from Example 5 wascooled to ambient temperature and its content was discharged to give aone phase system. A portion of the reaction solution (2 milliliters) wasextracted with acetonitrile (2 milliliters). The phases were separated,and the content of methyl 11-formylundecanoate product in each phase wasdetermined by gas chromatography. The partition coefficient of theproduct, as defined by Kpartition=amount of product in the heptanephase/amount of product in the acetonitrile phase, was determined to be0.19.

EXAMPLE 7

A solution of rhodium dicarbonyl acetylacetonate (10.1 milligrams; 0.039mmol) and Ligand B (98.1 milligrams; 0.117 mmol) in heptane (18 grams)was placed in a Parr reactor and activated for about 1 hour at 70° C.and 100 psi of syngas (CO/H₂ 1:1). Butyl 10-undecenoate (1.2 grams) andoctane (0.8 grams, internal standard) were charged to the autoclave andhydroformylated at 70° C. and 100 psi of syngas. The pressure of syngaswas maintained 100 psi during the course of reaction. The reaction wasfollowed by gas chromatography. After 20 hours the starting material wascompletely consumed and selectivity to the aldehyde products was 90%with the n/i ratio of 43.

EXAMPLE 8

The autoclave containing the hydroformylation mixture from Example 7 wascooled to room temperature and its contents were discharged to give aone phase system. A portion of the reaction solution (2 milliliters) wasextracted with acetonitrile (2 milliliters). The phases were separatedand the content of butyl 11-formylundecanoate product was determined inboth phases by gas chromatography. The partition coefficient of theproduct, as defined by Kpartition=amount of product in the heptanephase/amount of product in the acetonitrile phase, was determined to be0.56.

EXAMPLE 9

A solution of rhodium dicarbonyl acetylacetonate (30.3 mg; 0.117 mmol)and Ligand A (453 mg; 0.352 mmol) in heptane (24 g) was placed in a 160ml Parr reactor and activated for about 1 hour at 70° C. and 100 psi ofsyngas (CO/H₂ 1:1). Methyl 10-undecenoate (24 g; 121 mmol) and octane(12 g, internal standard) were charged to the autoclave.Hydroformylation was carried out at 70° C. and 100 psi of syngas withthe CO/H₂ ratio of 1:1. The reaction mixture was monitored by GC. After18 hrs the starting material was completely consumed and selectivity tothe aldehyde products was 86% with n/iso ratio of 35.

A portion of the reaction solution (5 mL) was diluted with heptane (10mL), shaken at room temperature under nitrogen with acetonitrle (13 mL)and allowed to settle. Two phases with approximately equal volumes wereanalyzed for rhodium and the hydroformylation product. The partitioncoefficient of the catalyst and the product defined as Kpartition=amountof material in the heptane phase/amount of material in the acetonitrilephase was determined for each component. Kpartition for rhodium wasfound to be 166, and Kpartition for the hydroformylation product wasfound to be 0.17. The extraction factor of the catalyst for one phaserelative to the product, defined as extraction factor=Kpartitionrhodium/Kpartition product was 976.

The solvent was removed from the acetonitrile layer, and the crudeproduct was crystallized from hexane (15 mL) at −5° C. to give 1.4 g(72% yield) of purified methyl 11-formylundecanoate with n/iso ratio of147.

¹H NMR spectrum in D-chloroform (chemical shifts in ppm are relative totrimethylsilane as external standard): 1.23 (m, 14 H, seven methylenegroups), 1.57 (m, 4H, two methylene groups), 2.25 (t, J=7.4 Hz, 2H, onemethylene group), 2.29 (doublet of triplets, J₁=7.4 Hz, J₂=1.8 Hz, 2H,one methylene group), 3.62 (s, 3H, methoxy group), 971 (t, J=1.8 Hz, 1H,aldehyde proton). ¹³C NMR spectrum in D-chloroform (chemical shifts inppm are relative to tetramethylsilane as external standard): 21.86,24.73, 28.91, 28.94, 29.01, 29.12, 29.41, 29.14, 33.86, 43.68 (tenmethylene groups), 51.23 (methoxy group), 174.10 (ester carbonyl group),202.70 (formyl group).

EXAMPLE 10

Methyl 11-formylundecanoate (1.0 g; 4.39 mmol), iso-propanol (20milliliters) and chromium modified Raney nickel (0.1 grams) were placedin a 80 milliliter Parr reactor and hydrogenated at 80° C. and 500 psiof hydrogen. After 2 hours, all the starting material was consumed, andthe reaction resulted in methyl 12-hydroxydodecanoate with 98%selectivity. The product was isolated as a white solid after filtration,solvent evaporation and drying in vacuum.

¹H NMR spectrum in D-chloroform (chemical shifts in ppm are relative totrimethylsilane as external standard): 1.26 (m, 14 H, seven methylenegroups), 1.55 (m, 2H, one methylene group), 1.60 (m, 2H, one methylenegroup), 1.69 (s, 1H, hydroxyl group), 2.29) (t, J=7.6 Hz, 2H, onemethylene group), 3.63 (t, J=6.7 Hz, 2H, one methylene group), 3.66 (s,3H, methoxy group).

¹³C NMR spectrum in D-chloroform (chemical shifts in ppm are relative totetramethylsilane as external standard): 24.87, 25.16, 29.06, 29.16,29.33, 29.34, 29.41, 29.48, 32.68, 34.04, 62.94 (eleven methylenegroups), 51.40 (methoxy group), 174.33 (ester carbonyl group).

EXAMPLE 11

Air was sparged in a solution of methyl 11-formylundecanoate (1.0 gram;4.39 mmol) in heptane (20 milliliters) at 50° C. The reaction wasfollowed by gas chromatography. After 3 hours, greater than 97% of thestarting material was oxidized. The product was crystallized from thesame solution at room temperature and isolated as a white solid withgreater than 99.5% purity.

¹H NMR spectrum in D-chloroform (chemical shifts in ppm are relative totetramethylsilane as external standard): 1.27 (m, 12 H, six methylenegroups), 1.60 (m, 4H, two methylene group), 2.30 (t, J=7.7 Hz, 2H, onemethylene group), 2.34 (t, J=7.5 Hz, 2H, one methylene group), 3.66 (s,3H methoxy group).

EXAMPLE 12

Methyl 11-formylundecanoate (1.4 grams; 6.14 mmol) in methanol (5milliliters) was placed at room temperature in a 160 milliliter Parrreactor containing methanol (60 milliliters) ammonia (3.13 grams; 184mmol) and nickel (65 wt. %) on silica/alumina (0.5 grams) and stirredfor 10 minutes. Then hydrogen was charged and the reaction continued at6° C. and 1,000 psi. Analysis by gas chromatography after 20 hoursshowed that all the starting material was consumed, and the reactionresulted in methyl 12-aminododecanoate in 91% yield. The catalyst wasseparated by filtration, the solvent was evaporated and a crude productwas purified by crystallization from hexane.

¹H NMR spectrum in D-ethanol (chemical shifts in ppm are relative totetramethylsilane as external standard): 1.30 (m, 14 H, eight methylenegroups), 1.59 (m, 4H, two methylene groups), 2.29 (t, J=7.5 Hz, 2H, onemethylene group), 3.62 (s, 3H, methoxy group). Mass spectrum: 229 (M⁺).

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A process for separating one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof, from a reaction productfluid comprising one or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products, a nonpolar solvent and a polarsolvent, wherein said process comprises (1) mixing said reaction productfluid to obtain by phase separation a nonpolar phase comprising said oneor more unreacted unsaturated reactants, said metal-organophosphorusligand complex catalyst, said optionally free organophosphorus ligandand sail nonpolar solvent and a polar phase comprising said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products and said polar solvent, and (2)recovering said polar phase from said nonpolar phase; wherein (i) theselectivity of the nonpolar phase for the organophosphorus ligand withrespect to the one or more products is expressed by the followingpartition coefficient ratio Ef1: ${Ef1} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp2}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {products}}\end{matrix}}$

in which said partition coefficient Kp1 is the ratio of theconcentration of organophosphorus ligand in the nonpolar phase afterextraction to the concentration of organophosphorus ligand in the polarphase after extraction, said partition coefficient Kp2 is the ratio ofthe concentration of products in the nonpolar phase after extraction tothe concentration of products in the polar phase after extraction, andsaid Ef1 is a value greater than about 2.5, (ii) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more organophosphorus ligand degradation products is expressed by thefollowing partition coefficient ratio Ef2: ${Ef2} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp3}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {organophosphorus}} \\{{ligand}\quad {degradation}\quad {products}}\end{matrix}}$

in which said partition coefficient Kp1 is as defined above, saidpartition coefficient Kp3 is the ratio of the concentration oforganophosphorus ligand degradation products in the nonpolar phase afterextraction to the concentration of organophosphorus ligand degradationproducts in the polar phase after extraction, and said Ef2 is a valuegreater than about 2.5, and (iii) the selectivity of the nonpolar phasefor the organophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the following partition coefficient ratioEf3: ${Ef3} = \frac{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp1}} \\{{of}\quad {organophosphorus}\quad {ligand}}\end{matrix}}{\begin{matrix}{{Partition}\quad {coefficient}\quad {Kp4}} \\{{of}\quad {one}\quad {or}\quad {more}\quad {reaction}} \\{{by}{products}}\end{matrix}}$

in which said partition coefficient Kp1 is as defined above, saidpartition coefficient Kp4 is the ratio of the concentration of reactionbyproducts in the nonpolar phase after extraction to the concentrationof reaction byproducts in the polar phase after extraction, and said Ef3is a value greater than about 2.5.
 2. A process for separating one ormore organophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof, from a reaction productfluid comprising one or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products and a nonpolar solvent, whereinsaid process comprises (1) mixing said reaction product fluid with apolar solvent to obtain by phase separation a nonpolar phase comprisingsaid one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand and said nonpolar solvent and a polar phasecomprising said one or more organophosphorus ligand degradationproducts, said one or more reaction byproducts, said one or moreproducts and said polar solvent, and (2) recovering said polar phasefrom said nonpolar phase, wherein (i) the selectivity of the nonpolarphase for the organophosphorus ligand with respect to the one or moreproducts is expressed by the partition coefficient ratio Ef1 defined inclaim 1 which is a value greater than about 2.5), (ii) the selectivityof the nonpolar phase for the organophosphorus ligand with respect tothe one or more organophosphorus ligand degradation products isexpressed by the partition coefficient ratio Ef2 defined in claim 1which is a value greater than about 2.5, and (iii) the selectivity ofthe nonpolar phase for the organophosphorus ligand with respect to theone or more reaction byproducts is expressed by the partitioncoefficient ratio Ef3 defined in claim 1 which is a value greater thanabout 2.5.
 3. A process for producing one or more products, saidproducts comprising one or more formylesters and/or derivatives thereof,comprising: (1) reacting one or more unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, in the presence of a metal-organophosphorus ligandcomplex catalyst, optionally free organophosphorus ligand, a nonpolarsolvent and a polar solvent to form a multiphase reaction product fluid,and (2) separating said multiphase reaction product fluid to obtain atleast one nonpolar phase comprising one or more unreacted unsaturatedreactants, said metal-organophosphorus ligand complex catalyst, saidoptionally free organophosphorus ligand and said nonpolar solvent and atleast one polar phase comprising one or more organophosphorus liganddegradation products, one or more reaction byproducts, said one or moreproducts and said polar solvent; wherein (i) the selectivity of the atleast one nonpolar phase for the organophosphorus ligand with respect tothe one or more products is expressed by the partition coefficient ratioEf1 defined in claim 1 which is a value greater than about 2.5, (ii) theselectivity of the at least one nonpolar phase for the organophosphorusligand with respect to the one or more organophosphorus liganddegradation products is expressed by the partition coefficient ratio Ef2defines in claim 1 which is a value greater than about 2.5, and (iii)the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the partition coefficient ratio Ef3 definedin claim 1 which is a value greater than about 2.5.
 4. A process forproducing one or more products, said products comprising one or moreformylesters and/or derivatives thereof, comprising: (1) reacting one ormore unsaturated reactants, said unsaturated reactants comprising one ormore unsaturated esters and/or derivatives thereof in the presence of ametal-organophosphorus ligand complex catalyst, optionally freeorganophosphorus ligand and a nonpolar solvent to form a reactionproduct fluid; (2) mixing said reaction product fluid with a polarsolvent to form a multiphase reaction product fluid; and (3) separatingsaid multiphase reaction product fluid to obtain at least one nonpolarphase comprising one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst said optionally freeorganophosphorus ligand and said nonpolar solvent, and at least onepolar phase comprising one or more organophosphorus ligand degradationproducts, one or more reaction byproducts, said one or more products andsaid polar solvent; wherein (i) the selectivity of the at least onenonpolar phase for the organophosphorus ligand with respect to the oneor more products is expressed by the partition coefficient ratio Ef1defined in claim 1 which is a value greater than about 2.5, (ii) theselectivity of the at least one nonpolar phase for the organophosphorusligand with respect to the one or more organophosphorus liganddegradation products is expressed by the partition coefficient ratio Ef2defined in claim 1 which is a value greater than about 2.5. and (iii)the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the partition coefficient ratio Ef3 definedin claim 1 which is a value greater than about 2.5.
 5. A process forseparating one or more organophosphorus ligand degradation products, oneor more reaction byproducts and one or more products, said productscomprising one or more formylesters and/or derivatives thereof, from areaction product fluid comprising one or more unreacted unsaturatedreactants, said unsaturated reactants comprising one or more unsaturatedesters and/or derivatives thereof, a metal-organophosphorus ligandcomplex catalyst, optionally free organophosphorus ligand, said one ormore organophosphorus ligand degradation products said one or morereaction byproducts, said one or more products, a first nonpolar solventand a second nonpolar solvent, wherein said process comprises (1) mixingsaid reaction product fluid to obtain by phase separation a nonpolarphase comprising said one or more unreacted unsaturated reactants, saidmetal-organophosphorus and complex catalyst, said optionally freeorganophosphorus ligand, said first nonpolar solvent and said secondnonpolar solvent and a polar phase comprising said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts and said one or more products, and (2) recovering said polarphase from said nonpolar phase; wherein (i) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more products is expressed by the partition coefficient ratio Ef1defined in claim 1 which is a value greater than about 2.5), (ii) theselectivity of the nonpolar phase for the organophosphorus ligand withrespect to the one or more organophosphorus ligand degradation productsis expressed by the partition coefficient ratio Ef2 defined in claim 1which is a value greater than about 2.5, and (iii) the selectivity ofthe nonpolar phase for the organophosphorus ligand with respect to theone or more reaction byproducts is expressed by the partitioncoefficient ratio Ef3 defined in claim 1 which is a value greater thanabout 2.5.
 6. A process for separating one or more organophosphorusligand degradation products, one or more reaction byproducts and one ormore products, said products comprising one or more formylesters and/orderivatives thereof, from a reaction product fluid comprising one ormore unreacted unsaturated reactants, said unsaturated reactantscomprising one or more unsaturated esters and/or derivatives thereof, ametal-organophosphorus ligand complex catalyst, optionally fleeorganophosphorus ligand, said one or more organophosphorus liganddegradation products, said one or more reaction byproducts, said one ormore products and a first nonpolar solvent, wherein said processcomprises (1) mixing said reaction product fluid with a second nonpolarsolvent to obtain by phase separation a nonpolar phase comprising saidone or more unreacted unsaturated reactants, said metal-organophosphorusligand complex catalyst, said optionally free organophosphorus ligand,said first nonpolar solvent and said second nonpolar solvent and a polarphase comprising said one or more organophosphorus ligand degradationproducts, said one or more reaction byproducts and said one or moreproducts, and (2) recovering said polar phase from said nonpolar phase;wherein (i) the selectivity of the nonpolar phase for theorganophosphorus ligand with respect to the one or more products isexpressed by the partition coefficient ratio Ef1 defined in claim 1which is a value greater than about 2.5, (ii) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more organophosphorus ligand degradation products is expressed by thepartition coefficient ratio Ef2 defined in claim 1 which is a valuegreater than about 2.5, and (iii) the selectivity of the nonpolar phasefor the organophosphorus ligand with respect to the one or more reactionbyproducts is expressed by the partition coefficient ratio Ef3 definedin claim 1 which is a value greater than about 2.5.
 7. A process forproducing one or more products, said products comprising one or moreformylesters and/or derivatives thereof, comprising: (1) reacting one ormore unsaturated reactants, said unsaturated reactants comprising one ormore unsaturated esters and/or derivatives thereof, in the presence of ametal-organophosphorus ligand complex catalyst, optionally freeorganophosphorus ligand, a first nonpolar solvent and a second nonpolarsolvent to form a multiphase reaction product fluid; and (2) separatingsaid multiphase reaction product fluid to obtain at least one nonpolarphase comprising one, or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand, said first nonpolar solvent and said secondnonpolar solvent and at least one polar phase comprising one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and said one or more products; wherein (i) the selectivity ofthe at least one nonpolar phase for the organophosphorus ligand withrespect to the one or more products is expressed by the partitioncoefficient ratio Ef1 defined in claim 1 which is a value greater thanabout 2.5, (ii) the selectivity of the at least one nonpolar phase forthe organophosphorus ligand with respect to the one or moreorganophosphorus ligand degradation products is expressed by thepartition coefficient ratio Ef2 defined in claim 1 which is a valuegreater than about 2.5, and (iii) the selectivity of the at least onenonpolar phase for the organophosphorus ligand with respect to the oneor more reaction byproducts is expressed by the partition coefficientratio Ef3 defined in claim 1 which is a value greater than about 2.5. 8.A process for producing one or more products, said products comprisingone or more formylesters and/or derivatives thereof, comprising: (1)reacting one or more unsaturated reactants, said unsaturated reactantscomprising one or more unsaturated esters and/or derivatives thereof, inthe presence of a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand and a first nonpolar solvent toform a reaction product fluid; (2) mixing said reaction product fluidwith a second nonpolar solvent to form a multiphase reaction productfluid; and (3) separating said multiphase reaction product fluid toobtain at least one nonpolar phase comprising one or more unreactedunsaturated reactants, said metal-organophosphorus ligand complexcatalyst, said optionally free organophosphorus ligand, said firstnonpolar solvent and said second nonpolar solvent and at least one polarphase comprising one or more organophosphorus ligand degradationproducts, one or more reaction byproducts and said one or more products;wherein (i) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more products isexpressed by the partition coefficient ratio Ef1 defined in claim 1which is a value greater than about 2.5, (ii) the selectivity of the atleast one nonpolar phase for the organophosphorus ligand with respect tothe one or more organophosphorus ligand degradation products isexpressed by the partition coefficient ratio Ef2 defined in claim 1which is a value greater than about 2.5. and (iii) the selectivity ofthe at least one nonpolar phase for the organophosphorus ligand withrespect to the one or more reaction byproducts is expressed by thepartition coefficient ratio Ef3 defined in claim l which is a valuegreater than about 2.5.
 9. A process for separating one or moreorganophosphorus ligand degradation products, one or more reactionbyproducts and one or more products, said products comprising one ormore formylesters and/or derivatives thereof, from a reaction productfluid comprising one, or more unreacted unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, a metal-organophosphorus ligand complex catalyst,optionally free organophosphorus ligand, said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts, said one or more products and a nonpolar solvent, whereinsaid process comprises (1) mixing said reaction product fluid to obtainby phase separation a nonpolar phase comprising said one or moreunreacted unsaturated reactants, said metal-organophosphorus ligandcomplex catalyst, said optionally free organophosphorus ligand and saidnonpolar solvent and a polar phase comprising said one or moreorganophosphorus ligand degradation products, said one or more reactionbyproducts and said one or more products, and (2) recovering said polarphase from said nonpolar phase; wherein (i) the selectivity of thenonpolar phase for the organophosphorus ligand with respect to the oneor more products is expressed by the partition coefficient ratio Ef1defined in claim 1 which is a value greater than about 2.5, (ii) theselectivity of the nonpolar phase for the organophosphorus ligand withrespect to the one or more organophosphorus ligand degradation productsis expressed by the partition coefficient ratio Ef2 defined in claim 1which is a value greater than about 2.5, and (iii) the selectivity ofthe nonpolar phase for the organophosphorus ligand with respect to theone or more reaction byproducts is expressed by the partitioncoefficient ratio Ef3 defined in claim 1 which is a value greater thanabout 2.5.
 10. A process for producing one or more products, saidproducts comprising one or more formylesters and/or derivatives thereof,comprising: (1) reacting one or more unsaturated reactants, saidunsaturated reactants comprising one or more unsaturated esters and/orderivatives thereof, in the presence of a metal-organophosphorus ligandcomplex catalyst, optionally free organophosphorus ligand and a nonpolarsolvent to form a multiphase reaction product fluid; and (2) separatingsaid multiphase reaction product fluid to obtain at least one nonpolarphase comprising one or more unreacted unsaturated reactants, saidmetal-organophosphorus ligand complex catalyst, said optionally freeorganophosphorus ligand and said nonpolar solvent and at least one polarphase comprising one or more organophosphorus ligand degradationproducts, one or more reaction byproducts and said one or more products;wherein (i) the selectivity of the at least one nonpolar phase for theorganophosphorus ligand with respect to the one or more products isexpressed by the partition coefficient ratio Ef1 defined in claim 1which is a value greater than about 2.5, (ii) the selectivity of the atleast one nonpolar phase for the organophosphorus ligand with respect tothe one or more organophosphorus ligand degradation products isexpressed by the partition coefficient ratio Ef2 defined in claim 1which is a value greater than about 2.5. and (iii) the selectivity ofthe at least one, nonpolar phase for the organophosphorus ligand withrespect to the one or more reaction byproducts is expressed by thepartition coefficient ratio Ef3 defined in claim 1 which is a valuegreater than about 2.5.
 11. The process of claim 1 wherein Ef1 is avalue of greater than about 3.0, Ef2 is a value of greater than about3.0, and Ef3 is a value of greater than about 3.0.
 12. The process ofclaim 1 wherein the one or more unsaturated esters comprise esters ofundecenoic acid.
 13. The process of claim 12 wherein the one or moreesters of undecenoic acid are derived from castor oil.
 14. The processof claim 1 wherein said nonpolar solvent is selected from alkanes,cycloalkanes, alkenes, aldehydes, ketones, ethers, esters, amines,aromatics, silanes, silicones, carbon dioxide, and mixtures thereof. 15.The process of claim 1 wherein said polar solvent is selected fromnitrites, lactones, alkanols, cyclic acetals, pyrrolidones, formamides,sulfoxides, and mixtures thereof.
 16. The process of claim 14 whereinsaid nonpolar solvent is selected from propane, 2,2-dimethylpropane,butane, 2,2-dimethylbutane, pentane, isopropyl ether, hexane,triethylamine, heptane, octane, nonane, decane, isobutyl isobutyrate,tributylamine, undecane, 2,2,4-trimethylpentyl acetate, isobutyl heptylketone, diisobutyl ketone, cyclopentane, cyclohexane, isobutylbenzene,n-nonylbenzene, n-octylbenzene, n-butylbenzene, p-xylene, ethylbenzene,1,3,5-trimethylbenzene, m-xylene, toluene, o-xylene, decene, dodecene,tetradecene, heptadecanal, and mixtures thereof.
 17. The process ofclaim 15 wherein said polar solvent is selected from propionitrile,1,3-dioxolane, 3-methoxypropionitrile, 1-methyl-2-pyrrolidinone,N,N-dimethylformamide, 2-methyl-2-oxazoline, adiponitrile, acetonitrile,epsilon caprolactone, glutaronitrile, 3-methyl-2-oxazolidinone, dimethylsulfoxide, sulfolane, and mixtures thereof.
 18. The process of claim 1wherein said metal-organophosphorus ligand complex catalyst comprisesrhodium complexed with an organophosphorus ligand represented by theformula: (i) a triorganophosphine ligand represented by the formula:

wherein R¹ is the same or different and represents a substituted orunsubstituted monovalent hydrocarbon radical containing from 1 to 24carbon atoms or 1 greater; (ii) a monoorganophosphite represented by theformula:

wherein R³ represents a substituted or unsubstituted trivalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater;(iii) a diorganophosphite represented by the formula:

wherein R⁴ represents a substituted or unsubstituted divalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater andW represents a substituted or unsubstituted monovalent hydrocarbonradical containing from 1 to 18 carbon atoms or greater; (iv) atriorganophosphite represented by the formula:

wherein each R⁸ is the same or different and represents a substituted orunsubstituted monovalent hydrocarbon radical; and (v) anorganopolyphosphite containing two or more tertiary (trivalent)phosphorus atoms represented by the formula:

wherein X¹ represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁹ is the same or different and represents a divalent hydrocarbonradical containing from 4 to 40 carbon atoms, each R¹⁰ is the same ordifferent and represents a substituted or unsubstituted monovalenthydrocarbon radical containing from 1 to 24 carbon atoms, a and b can bethe same or different and each have a value of 0 to 6, with the provisothat the sum of a+b is 2 to 6 and n equals a+b.
 19. A reaction mixturecomprising one or more substituted or unsubstituted products, saidproducts comprising one or more formylesters and/or derivatives thereof,in which said reaction mixture is prepared by the process of claim 3.20. The process of claim 3 further comprising derivatizing the one ormore formylesters.
 21. The process of claim 20 in which the derivatizingreaction comprises hydrogenation, esterification, etherification,amination, alkylation, dehydrogenation, reduction, acylation,condensation, carboxylation, carbonylation, oxidation, cyclization,reductive amination, silylation, hydrolysis, polymerization,copolymerization and permissible combinations thereof.
 22. The processof claim 3 further comprising subjecting said one or more formylestersto reductive amination optionally in the presence of a reductiveamination catalyst to produce one or more aminoesters, subjecting saidone or more aminoesters to hydrolysis optionally in the presence of ahydrolysis catalyst to produce one or more aminoacids, and subjectingsaid one or more aminoacids to polymerization to produce one or morepolyamides.
 23. The process of claim 3 further comprising subjectingsaid one or more formylesters to oxidation optionally in the presence ofan oxidation catalyst to produce one or more acidoesters, subjectingsaid one or more acidoesters to hydrolysis optionally in the presence ofa hydrolysis catalyst to produce one or more diacids, and subjectingsaid one or more diacids to copolymerization with one or more diaminesto produce one or more polyamides.
 24. The process of claim 3 furthercomprising subjecting said one or more formylesters to hydrogenationoptionally in the presence of a hydrogenation catalyst to produce one ormore ester alcohols and/or one or more diols.